Piezoelectric material filler, composite piezoelectric material, composite piezoelectric device, composite piezoelectric material filler, and method for producing alkali niobate compound

ABSTRACT

Provided is a piezoelectric material filler including alkali niobate compound particles having a ratio (K/(Na+K)) of the number of moles of potassium to the total number of moles of sodium and potassium of 0.460 to 0.495 in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles of alkali metal elements to the number of moles of niobium of 0.995 to 1.005 in terms of atoms. The present invention can provide a piezoelectric material filler having excellent piezoelectric properties, and a composite piezoelectric material including the piezoelectric material filler and a polymer matrix.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.16/310,988, filed on Dec. 18, 2018, which is a 371 of InternationalApplication No. PCT/JP2017/022533, filed on Jun. 19, 2017, which isbased upon and claims the benefit of priority from the prior JapanesePatent Application No. 2016-124284, filed on Jun. 23, 2016, JapanesePatent Application No. 2016-124285, filed on Jun. 23, 2016, JapanesePatent Application No. 2016-124286, filed on Jun. 23, 2016, JapanesePatent Application No. 2016-221324, filed on Nov. 14, 2016, JapanesePatent Application No. 2017-110787, filed on Jun. 5, 2017, JapanesePatent Application No. 2017-110788, filed on Jun. 5, 2017, JapanesePatent Application No. 2017-110789, filed on Jun. 5, 2017, JapanesePatent Application No. 2017-118243, filed on Jun. 16, 2017, JapanesePatent Application No. 2017-118244, filed on Jun. 16, 2017 and JapanesePatent Application No. 2017-118245, filed on Jun. 16, 2017, the entirecontents of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a piezoelectric material filler, acomposite piezoelectric material using the piezoelectric materialfiller, and a composite piezoelectric device using the same.

Further, the present invention relates to a composite piezoelectricmaterial filler that is used as a filler of a composite piezoelectricmaterial comprising a polymer matrix and a filler dispersed in thematrix, a composite piezoelectric material using the compositepiezoelectric material filler, and a composite piezoelectric deviceusing the same.

Further, the present invention relates to a method for producing analkali niobate compound that is used as a piezoelectric ceramic rawmaterial for sintering production or a composite piezoelectric materialfiller of a composite piezoelectric material in which a filler a forcomposite piezoelectric material is contained and dispersed in a polymermatrix.

BACKGROUND ART

Conventionally, lead zirconate titanate having good piezoelectricproperties has been often used as piezoelectric ceramics used forpiezoelectric devices, sensors, or the like. However, in recent years,development of lead-free materials without using lead is required due tothe growing interest in environmental pollution. Among lead-freematerials, niobate piezoelectric ceramics having comparatively excellentpiezoelectric properties have been researched.

Examples of the niobate piezoelectric ceramics include niobate ceramicsof alkali metals such as Li, Na, and K. For example, Patent Literature 1discloses alkali niobate piezoelectric ceramics represented by AMO₃(where A represents an alkali metal, M represents Nb, and 0 representsoxygen). Further, Patent Literature 2 discloses potassium sodium niobatelead-free piezoelectric ceramics represented by(1−n)K_(x)Na_(1−x)NbO₃.nMH (where MH represents a metal oxide or a metalcarbonate, M represents a metal element having a different valence, Hrepresents an 0 or CO₃ radical, 0.2≤x≤0.95, and 0≤n≤0.30). Further,Patent Literature 3 discloses piezoelectric ceramics of KNbO₃ ceramics.

Further, Patent Literature 4 and Patent Literature 5 disclose compositepiezoelectric materials in which piezoelectric particles are dispersedin a polymer matrix, for example.

CITATION LIST Patent Literature Patent Literature 1: Japanese PatentApplication Laid-Open No. 2011-236091 Patent Literature 2: JapanesePatent Application Laid-Open No. 2007-22854 Patent Literature 3:Japanese Patent Application Laid-Open No. 2010-241658 Patent Literature4: Japanese Patent Application Laid-Open No. 2012-142546 PatentLiterature 5: Japanese Patent Application Laid-Open No. 2015-50432SUMMARY OF INVENTION Technical Problem

Examples of the niobate piezoelectric ceramics include niobate ceramicsof alkali metals such as Li, Na, and K, as described above, whereattempts to adjust the composition ratio of alkali metals have been madein order to achieve excellent piezoelectric properties, but sufficientpiezoelectric properties could not have been achieved yet. Further, alsofor the composite piezoelectric materials in which piezoelectricparticles are dispersed in a polymer matrix, optimization of thecomposition ratio of alkali metals for achieving excellent piezoelectricproperties in the niobate alkali metal compound used as thepiezoelectric particles is still being discussed.

Accordingly, it is an object of the present invention to provide apiezoelectric material filler having excellent piezoelectric propertiesby adjusting the composition ratio of alkali metals in a niobate alkalimetal compound and to provide a composite piezoelectric material usingthe piezoelectric material filler.

Further, the aforementioned piezoelectric ceramics have difficulty informability. In contrast, examples of piezoelectric materials havingexcellent formability include composite piezoelectric materials in whichpiezoelectric particles are dispersed in a polymer matrix, and compositepiezoelectric materials comprising a polymer matrix are expected to beused in applications in which conventional piezoelectric ceramics havenot been used, because of their good formability.

However, Patent Literature 4 and Patent Literature 5, for example,disclose composite piezoelectric materials in which piezoelectricparticles are dispersed in a polymer matrix, as such compositepiezoelectric materials, but the composite piezoelectric materials inwhich piezoelectric particles are dispersed in a polymer matrix have notbeen studied sufficiently so far. Therefore, development of compositepiezoelectric materials comprising a polymer matrix having excellentpiezoelectric properties has been desired.

Accordingly, it is an object of the present invention to provide acomposite piezoelectric material comprising a polymer matrix havingexcellent piezoelectric properties and to provide a compositepiezoelectric material filler used for the composite piezoelectricmaterial.

Further, in production of conventional alkali niobate compounds, whenalkali compounds and a niobium compound are dry-mixed and fired, thealkali compounds deliquesce, thereby making uniform mixing difficult.Therefore, there has been a problem that the molar ratio of the alkalimetals in the composite metal oxide obtained by firing deviates from adesired molar ratio, and precise adjustment of the molar ratio of thealkali metals is difficult.

Accordingly, it is an object of the present invention to provide amethod for producing an alkali niobate compound by dry-mixing firing rawmaterials, the method enabling precise adjustment of the molar ratio ofalkali metals.

Solution to Problem

The aforementioned problem is solved by the present invention below.

(1) A piezoelectric material filler comprising alkali niobate compoundparticles having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.460 to 0.495in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total number ofmoles of alkali metal elements to the number of moles of niobium of0.995 to 1.005 in terms of atoms.(2) The piezoelectric material filler according to (1), wherein thealkali niobate compound particles have an average particle size of 0.1to 15 μm.(3) The piezoelectric material filler according to (1) or (2), wherein aratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the alkali niobate compoundparticles is 0 or more and less than 0.10 in terms of atoms.(4) A composite piezoelectric material comprising:

the piezoelectric material filler according to any of (1) to (3); and

a polymer matrix.

(5) A composite piezoelectric device comprising:

the composite piezoelectric material according to (4) which has beenpolarized.

(6) A composite piezoelectric material comprising:

a polymer matrix; and

a piezoelectric material filler dispersed in the polymer matrix, wherein

the piezoelectric material filler comprises alkali niobate compoundparticles having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.460 to 0.495in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total number ofmoles of alkali metal elements to the number of moles of niobium of0.995 to 1.005 in terms of atoms.

(7) The composite piezoelectric material according to (6), wherein

a content of the composite piezoelectric material filler is 20 to 80 vol% based on the entire composite piezoelectric material.

(8) The composite piezoelectric material according to (6) or (7),wherein

a ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the alkali niobate compoundparticles is 0 or more and less than 0.10 in terms of atoms.

(9) A composite piezoelectric device comprising:

the composite piezoelectric material according to any of (6) to (8)which has been polarized.

(10) A composite piezoelectric material comprising:

a polymer matrix; and

a composite piezoelectric material filler dispersed in the polymermatrix, wherein

the composite piezoelectric material filler comprises:

-   -   a small-particle size filler comprising an alkali niobate        compound having a ratio (K/(Na+K)) of the number of moles of        potassium to the total number of moles of sodium and potassium        of 0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of        the total number of moles of alkali metal elements to the number        of moles of niobium of 0.995 to 1.005 in terms of atoms; and    -   a large-particle size filler comprising an alkali niobate        compound having a ratio (K/(Na+K)) of the number of moles of        potassium to the total number of moles of sodium and potassium        of 0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of        the total number of moles of alkali metal elements to the number        of moles of niobium of 0.995 to 1.005 in terms of atoms,    -   a total content of the small-particle size filler and the        large-particle size filler is 20 to 80 vol % based on the entire        composite piezoelectric material,    -   the small-particle size filler has an average particle size        (D50) of 0.1 to 1.2 μm,    -   the large-particle size filler has an average particle size        (D50) of 1 to 15 μm, and    -   a content ratio of the large-particle size filler to the        small-particle size filler (large-particle size        filler:small-particle size filler) is 10:90 to 90:10 by volume.        (11) The composite piezoelectric material according to (10),        wherein the small-particle size filler has a BET specific        surface area of 2 to 15 m²/g, and the large-particle size filler        has a BET specific surface area of 0.1 to 3 m²/g.        (12) The composite piezoelectric material according to (10) or        (11), wherein a ratio (large-particle size filler/small-particle        size filler) of the average particle size (D50) of the        large-particle size filler to the average particle size (D50) of        the small-particle size filler is 2 to 150.        (13) The composite piezoelectric material according to any        of (10) to (12), wherein

a ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the small-particle sizefiller is 0 or more and less than 0.10 in terms of atoms, and

a ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the large-particle sizefiller is 0 or more and less than 0.10 in terms of atoms.

(14) A composite piezoelectric device comprising:

the composite piezoelectric material according to any of (10) to (13)which has been polarized.

(15) A composite piezoelectric material comprising:

a polymer matrix; and

a composite piezoelectric material filler dispersed in the polymermatrix, wherein

the composite piezoelectric material filler comprises an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60 interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms,

a content of the alkali niobate compound is 20 to 80 vol % based on theentire composite piezoelectric material, and

the alkali niobate compound exhibits a bimodal particle sizedistribution including a first peak having a peak top in a particle sizerange of 0.1 to 1.2 μm and a second peak having a peak top in a particlesize range of 1 to 15 μm in a particle size distribution measurement,wherein a ratio (B/A) of a value (B) of a frequency (%) of a particlesize at the peak top of the second peak to a value (A) of a frequency(%) of a particle size at the peak top of the first peak is 0.1 to 20.

(16) The composite piezoelectric material according to (15), wherein aratio (the particle size at the peak top of the second peak/the particlesize at the peak top of the first peak) of the particle size at the peaktop of the second peak to the particle size at the peak top of the firstpeak is 2 to 150.(17) The composite piezoelectric material according to any of (15) or(16), wherein a ratio (Li/(Li+Na+K)) of the number of moles of lithiumto the total number of moles of alkali metal elements in the alkaliniobate compound is 0 or more and less than 0.10 in terms of atoms.(18) A composite piezoelectric device comprising:

the composite piezoelectric material according to any of (15) to (17)which has been polarized.

(19) A composite piezoelectric material filler comprising a mixture of:

a small-particle size filler comprising an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.40 to 0.60 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms; and

a large-particle size filler comprising an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.40 to 0.60 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, wherein

the small-particle size filler has an average particle size (D50) of 0.1to 1.2 μm,

the large-particle size filler has an average particle size (D50) of 1to 15 μm, and

a mixing ratio (large-particle size filler:small-particle size filler)of the large-particle size filler to the small-particle size filler is10:90 to 90:10 by volume.

(20) The composite piezoelectric material filler according to (19),wherein

the small-particle size filler has a BET specific surface area of 2 to15 m²/g, and

the large-particle size filler has a BET specific surface area of 0.1 to3 m²/g.

(21) The composite piezoelectric material filler according to (19) or(20), wherein a ratio (large-particle size filler/small-particle sizefiller) of the average particle size (D50) of the large-particle sizefiller to the average particle size (D50) of the small-particle sizefiller is 2 to 150.(22) The composite piezoelectric material filler according to any of(19) to (21), wherein a ratio (Li/(Li+Na+K)) of the number of moles oflithium to the total number of moles of alkali metal elements in thesmall-particle size filler is 0 or more and less than 0.10 in terms ofatoms, and a ratio (Li/(Li+Na+K)) of the number of moles of lithium tothe total number of moles of alkali metal elements in the large-particlesize filler is 0 or more and less than 0.10 in terms of atoms.(23) A composite piezoelectric material comprising:

the composite piezoelectric material filler according to any of (19) to(22); and

a polymer matrix.

(24) A composite piezoelectric device comprising:

the composite piezoelectric material according to (23) which has beenpolarized.

(25) A composite piezoelectric material filler comprising:

an alkali niobate compound having a ratio (K/(Na+K)) of the number ofmoles of potassium to the total number of moles of sodium and potassiumof 0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of thetotal number of moles of alkali metal elements to the number of moles ofniobium of 0.995 to 1.005 in terms of atoms,

the composite piezoelectric material filler exhibiting a bimodalparticle size distribution including a first peak having a peak top in aparticle size range of 0.1 to 1.2 μm and a second peak having a peak topin a particle size range of 1 to 15 μm in a particle size distributionmeasurement, wherein a ratio (B/A) of a value (B) of a frequency (%) ofa particle size at the peak top of the second peak to a value (A) of afrequency (%) of a particle size at the peak top of the first peak is0.1 to 20.

(26) The composite piezoelectric material filler according to (25),wherein a ratio (Li/(Li+Na+K)) of the number of moles of lithium to thetotal number of moles of alkali metal elements in the alkali niobatecompound is 0 or more and less than 0.10 in terms of atoms.(27) The composite piezoelectric material filler according to (25) or(26), wherein a ratio (the particle size at the peak top of the secondpeak/the particle size at the peak top of the first peak) of theparticle size at the peak top of the second peak to the particle size atthe peak top of the first peak is 2 to 150.(28) A composite piezoelectric material comprising:

the composite piezoelectric material filler according to any of (25) to(27); and

a polymer matrix.

(29) A composite piezoelectric device comprising:

the composite piezoelectric material according to (28) which has beenpolarized.

(30) A composite piezoelectric material filler used for the compositepiezoelectric material according to (10), the composite piezoelectricmaterial filler comprising an alkali niobate compound having a ratio(K/(Na+K)) of the number of moles of potassium to the total number ofmoles of sodium and potassium of 0.40 to 0.60 in terms of atoms and aratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium of 0.995 to 1.005 in terms ofatoms, and the composite piezoelectric material filler having an averageparticle size (D50) of 0.1 to 1.2 μm.(31) The composite piezoelectric material filler according to (30),wherein a ratio (Li/(Li+Na+K)) of the number of moles of lithium to thetotal number of moles of alkali metal elements in the alkali niobatecompound is 0 or more and less than 0.10 in terms of atoms.(32) A composite piezoelectric material filler used for the compositepiezoelectric material according to (10), the composite piezoelectricmaterial filler comprising an alkali niobate compound having a ratio(K/(Na+K)) of the number of moles of potassium to the total number ofmoles of sodium and potassium of 0.40 to 0.60 in terms of atoms and aratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium of 0.995 to 1.005 in terms ofatoms, and the composite piezoelectric material filler having an averageparticle size (D50) of 1 to 15 μm.(33) The composite piezoelectric material filler according to (32),wherein a ratio (Li/(Li+Na+K)) of the number of moles of lithium to thetotal number of moles of alkali metal elements in the alkali niobatecompound is 0 or more and less than 0.10 in terms of atoms.(34) A method for producing an alkali niobate compound having a ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of Nb of 0.995 to 1.005 in terms of atoms, themethod comprising:

a first step of dry-mixing alkali compounds and a niobium compound in anamount giving a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of Nb of 0.900 to 1.000 interms of atoms and a difference of a ratio (K/(Na+K)) of the number ofmoles of K to the total number of moles of Na and K from a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the alkali niobate compound as a production object fallingwithin ±0.015, to prepare a first firing raw material;

a second step of firing the first firing raw material at 500 to 750° C.,to obtain a first fired product;

a third step of dry-mixing alkali compounds with the first fired productin an amount giving a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of Nb of 0.995 to 1.005in terms of atoms and a difference of a ratio (K/(Na+K)) of the numberof moles of K to the total number of moles of Na and K from a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the alkali niobate compound as a production object fallingwithin ±0.010, to prepare a second firing raw material; and

a fourth step of firing the second firing raw material at 500 to 1000°C., to obtain the alkali niobate compound.

(35) The method for producing an alkali niobate compound according to(34), wherein the alkali compounds are any of Li₂CO₃, Na₂CO₃, and K₂CO₃,or a combination of any two or more of Li₂CO₃, Na₂CO₃, and K₂CO₃, andthe niobium compound is Nb₂O₅.(36) The method for producing an alkali niobate compound according to(34) or (35), wherein the first fired product obtained in the secondstep is ground to obtain a ground product.(37) The method for producing an alkali niobate compound according toany of (34) to (36), wherein the alkali niobate compound obtained in thefourth step is ground to obtain a ground product.(38) The method for producing an alkali niobate compound according toany of (34) to (37), wherein the alkali niobate compound obtained in thefourth step is further fired at 500 to 1000° C.(39) The method for producing an alkali niobate compound according toany of (34) to (38), wherein in the alkali niobate compound, the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K is 0 to 1.000 in terms of atoms, and a ratio (Li/(Li+Na+K)) ofthe number of moles of lithium to the total number of moles of alkalimetal elements is 0 to 0.100 in terms of atoms.

Advantageous Effects of Invention

The present invention can provide a piezoelectric material filler havingexcellent piezoelectric properties, and a composite piezoelectricmaterial comprising the piezoelectric material filler and a polymermatrix.

Further, the present invention can provide a composite piezoelectricmaterial comprising a polymer matrix having excellent piezoelectricproperties, and a composite piezoelectric material filler used for thecomposite piezoelectric material.

Further, the present invention can provide a method for producing analkali niobate compound by dry-mixing firing raw materials, the methodenabling precise adjustment of the molar ratio of alkali metals.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an XRD chart of potassium sodium niobate obtained in Example1.

FIG. 2 is a SEM photograph of the potassium sodium niobate obtained inExample 1.

FIG. 3 is an XRD chart of a small-particle size filler produced inProduction Example 1-1.

FIG. 4 is a SEM of the small-particle size filler produced in ProductionExample 1-1.

FIG. 5 is a particle size distribution curve of the small-particle sizefiller produced in Production Example 1-1.

FIG. 6 is an XRD chart of a large-particle size filler produced inProduction Example 2-1.

FIG. 7 is a SEM of the large-particle size filler produced in ProductionExample 2-1.

FIG. 8 is a particle size distribution curve of the large-particle sizefiller produced in Production Example 2-1.

FIG. 9 is a particle size distribution curve of a mixed compositepiezoelectric material filler A used in Example 11.

FIG. 10 is an XRD chart of a small-particle size filler produced inProduction Example 1-5.

FIG. 11 is a SEM of the small-particle size filler produced inProduction Example 1-5.

FIG. 12 is a particle size distribution curve of the small-particle sizefiller produced in Production Example 1-5.

FIG. 13 is an XRD chart of a large-particle size filler produced inProduction Example 2-5.

FIG. 14 is a SEM of the large-particle size filler produced inProduction Example 2-5.

FIG. 15 is a particle size distribution curve of the large-particle sizefiller produced in Production Example 2-5.

FIG. 16 is a particle size distribution curve of a mixed compositepiezoelectric material filler E used in Example 19.

FIG. 17 is a particle size distribution curve of a mixed compositepiezoelectric material filler F used in Example 20.

FIG. 18 is an XRD chart of potassium sodium niobate obtained in Example31.

FIG. 19 is a SEM of the potassium sodium niobate obtained in Example 31.

FIG. 20 is an XRD chart of lithium potassium sodium niobate obtained inExample 37.

FIG. 21 is a SEM of the lithium potassium sodium niobate obtained inExample 37.

DESCRIPTION OF EMBODIMENTS

A first invention of the present invention will be described.

<First Invention>

A piezoelectric material filler of the present invention comprisesalkali niobate compound particles having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.460 to 0.495 in terms of atoms and a ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005 in terms of atoms.

The piezoelectric material filler of the present invention is a fillerfor piezoelectric materials used for producing a composite piezoelectricmaterial comprising a polymer matrix and a filler by being contained anddispersed in the polymer matrix or used as a raw material for producingpiezoelectric ceramics.

In the alkali niobate compound particles according to the piezoelectricmaterial filler of the present invention, the ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium is 0.460 to 0.495, preferably 0.465 to 0.495, particularlypreferably 0.470 to 0.490, in terms of atoms. The ratio (K/(Na+K)) ofthe number of moles of potassium to the total number of moles of sodiumand potassium falling within the aforementioned ranges enhances thepiezoelectric properties.

In the alkali niobate compound particles according to the piezoelectricmaterial filler of the present invention, the ratio ((Li+Na+K)/Nb) ofthe total number of moles of alkali metal elements to the number ofmoles of niobium is 0.995 to 1.005, preferably 0.997 to 1.003, in termsof atoms.

The alkali niobate compound particles according to the piezoelectricmaterial filler of the present invention essentially contain sodium andpotassium as alkali compounds, and the alkali niobate compound particlesaccording to the piezoelectric material filler of the present inventionmay contain lithium for purposes such as improving the sinterability andcontrolling the variation of piezoelectric properties. In thecomposition ratio of lithium in the alkali niobate compound particles, aratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements is 0 or more and less than0.10, preferably 0 or more and less than 0.09, in terms of atoms, inorder not to impair the piezoelectric properties while achieving theaforementioned purposes.

The alkali niobate compound constituting the piezoelectric materialfiller of the present invention is a perovskite alkali niobate compoundrepresented by the following general formula (1):

ANbO₃  (1).

In the alkali niobate compound represented by the general formula (1), Aessentially contains sodium and potassium and may contain lithium, theratio (K/(Na+K)) of the number of moles of potassium to the total numberof moles of sodium and potassium is 0.460 to 0.495, preferably 0.465 to0.495, particularly preferably 0.470 to 0.490, in terms of atoms, andthe ratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium is 0.995 to 1.005, preferably0.997 to 1.003, in terms of atoms.

The piezoelectric material filler of the present invention is aparticulate alkali niobate compound. The average particle size of thealkali niobate compound particles according to the piezoelectricmaterial filler of the present invention is preferably 0.1 to 15 μm,particularly preferably 0.2 to 12 μm. In the present invention, theaverage particle size is a cumulative particle size at 50% (D50)determined in a volume frequency particle size distribution measurementmeasured by laser light scattering using MT3300EXII, manufactured byMicrotracBEL Corp.

The BET specific surface area of the alkali niobate compound particlesaccording to the piezoelectric material filler of the present inventionis preferably 0.1 to 15 m²/g, particularly preferably 0.2 to 10 m²/g.

The piezoelectric material filler of the present invention is suitablyproduced by a method for producing an alkali niobate compound accordingto the present invention described below.

The method for producing an alkali niobate compound according to thepresent invention is a method for producing an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.460 to 0.495 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, the method comprising: a first step ofdry-mixing alkali compounds and a niobium compound in an amount giving aratio ((Li+Na+K)/Nb) of the number of moles of alkali metal elements tothe number of moles of Nb of 0.900 to 1.000 in terms of atoms and adifference of a ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K from the ratio of the number of molesof K to the total number of moles of Na and K in the alkali niobatecompound as a production object falling within ±0.015, to prepare afirst firing raw material; a second step of firing the first firing rawmaterial at 500 to 750° C., to obtain a first fired product; a thirdstep of dry-mixing alkali compounds with the first fired product in anamount giving a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of Nb of 0.995 to 1.005 interms of atoms and a difference of a ratio (K/(Na+K)) of the number ofmoles of K to the total number of moles of Na and K from the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the alkali niobate compound as a production object fallingwithin ±0.010, to prepare a second firing raw material; and a fourthstep of firing the second firing raw material at 500 to 1000° C., toobtain the alkali niobate compound.

The first step is a step of dry-mixing alkali compounds and a niobiumcompound, to prepare a first firing raw material. The alkali compoundsaccording to the first step essentially contain both a sodium compoundand a potassium compound, and may contain a lithium compound, asrequired.

The sodium compound according to the first step is a compound having asodium atom, and examples thereof include sodium carbonate, sodiumhydrogencarbonate, sodium hydroxide, sodium oxalate, and sodiumtartrate. The sodium compound may be of one type or a combination of twoor more types. As the sodium compound, sodium carbonate (Na₂CO₃) ispreferable for good handleability and good reactivity. Further, a higherpurity of the sodium compound is preferable.

The average particle size (D50) of the sodium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the sodium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the sodium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the sodiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The potassium compound according to the first step is a compound havinga potassium atom, and examples thereof include potassium carbonate,potassium hydrogencarbonate, potassium hydroxide, potassium oxalate, andpotassium tartrate. The potassium compound may be of one type or acombination of two or more types. As the potassium compound, potassiumcarbonate (K₂CO₃) is preferable for good handleability and goodreactivity throughout blending to firing. Further, a higher purity ofthe potassium compound is preferable.

The average particle size (D50) of the potassium compound according tothe first step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the potassium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the potassium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the potassiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The lithium compound according to the first step is a compound having alithium atom, and examples thereof include lithium carbonate, sodiumhydrogencarbonate, lithium hydroxide, lithium oxalate, and lithiumtartrate. The lithium compound may be of one type or a combination oftwo or more types. As the lithium compound, lithium carbonate (Li₂CO₃)is preferable for good handleability and good reactivity. Further, ahigher purity of the lithium compound is preferable.

The average particle size (D50) of the lithium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the lithium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the lithium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the lithiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The niobium compound according to the first step is a compound having aniobium atom, and examples thereof include niobium pentoxide, niobiumhydroxide, and ammonium niobium oxalate. The niobium compound may be ofone type or a combination of two or more types. As the niobium compound,niobium pentoxide (Nb₂O₅) is preferable for easy handleability and goodprecise composition control. Further, a higher purity of the niobiumcompound is preferable.

The average particle size (D50) of the niobium compound according to thefirst step is not particularly limited, and is preferably 0.1 to 15 μm,particularly preferably 0.2 to 12 μm. The average particle size (D50) ofthe niobium compound falling within the aforementioned ranges increasesthe mixability with other raw materials and facilitates the adjustmentof the composition, thereby enabling effective reaction in firing, whichwill be described below. Further, the BET specific surface area of theniobium compound according to the first step is not particularlylimited, and is preferably 0.1 to 15 m²/g, particularly preferably 0.2to 10 m²/g. The BET specific surface area of the niobium compoundfalling within the aforementioned ranges enables production of an alkaliniobate compound having excellent dispersibility and good crystallinityeven in the dry method. The average particle size in the presentinvention is a cumulative particle size at 50% (D50) determined in avolume frequency particle size distribution measurement measured bylaser light scattering using MT3300EXII, manufactured by MicrotracBELCorp.

In the first step, the first firing raw material is obtained bydry-mixing the alkali compounds and the niobium compound in an amountgiving a ratio ((Li+Na+K)/Nb) of the total number of moles of alkalimetal elements to the number of moles of Nb of 0.900 to 1.000,preferably 0.920 to 0.995, in terms of atoms and a difference of a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K from the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the alkali niobate compound as aproduction object falling within ±0.015. That is, in the first step, theamount of the alkali metal elements in the first firing raw material ismade equimolar to Nb or slightly less than the equimolar amount to Nb.Further, in the first step, the ratio of the amounts of Na and K in thefirst firing raw material is made equivalent to the molar ratio of Naand K in the alkali niobate compound as a production object. The alkaliniobate compound as a production object is an alkali niobate compoundthat is intended to be obtained by performing the method for producingan alkali niobate compound according to the present invention. When thealkali niobate compound as a production object is an alkali niobatecompound containing lithium, a lithium compound as an alkali compoundmay be mixed or not mixed to the first firing raw material in the firststep, as long as the ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of Nb is 0.900 to 1.000,preferably 0.920 to 0.995, in terms of atoms. When the alkali niobatecompound as a production object is an alkali niobate compound containinglithium, a lithium compound as an alkali compound is mixed with thefirst firing raw material in the first step, and lithium atoms are shortas compared with those in the alkali niobate compound as a productionobject, a lithium compound is mixed with the second firing raw materialin the third step in an amount corresponding to the shortage of lithiumatoms. Meanwhile, when the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, and a lithiumcompound as an alkali compound is not mixed with the first firing rawmaterial in the first step, a lithium compound is mixed with the secondfiring raw material in the third step in such a way as to give thecontent of lithium atoms in the alkali niobate compound as a productionobject.

In the present invention, the phrase, the difference of the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the first firing raw material from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falls within ±0.015,means that, when the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the first firing raw material interms of atoms is referred to as Y, and the ratio (K/(Na+K)) of thenumber of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object is referred to as Z, thevalue “Y−Z” falls within ±0.015. For example, when producing an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K of 0.45, the ratio (K/(Na+K))of the number of moles of K to the total number of moles of Na and K inthe first firing raw material is set to a molar ratio of 0.435 to 0.465in terms of atoms. Further, the same applies to the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thesecond firing raw material, which will be described below.

In the first step, alkali compounds and a niobium compound aredry-mixed. The dry-mixing method is not particularly limited, andexamples thereof include mixing methods using a blender, a ribbon mixer,a Henschel mixer, a food mixer, a super mixer, a Nauta mixer, a Juliamixer, or the like.

The second step is a step of firing the first firing raw materialobtained by performing the first step, to obtain a first fired product.

In the second step, the firing temperature when firing the first firingraw material is 500 to 750° C., preferably 550 to 700° C. Further, inthe second step, the firing time when firing the first firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the second step is performed to obtain the first fired product,the obtained first fired product may be ground, as required. Forgrinding the first fired product, grinding devices such as a jet mill, aball mill, a bead mill, an ultimizer, an atomizer, a nanomizer, apulverizer, and a pin mill can be used.

The third step is a step of dry-mixing alkali compounds with the firstfired product obtained by performing the second step, to prepare asecond firing raw material.

The alkali compounds according to the third step are the same as thealkali compounds according to the first step. The sodium compound usedin the third step may be the same as the sodium compound used in thefirst step or may be different from the sodium compound used in thefirst step. Further, the potassium compound used in the third step maybe the same as the potassium compound used in the first step or may bedifferent from the potassium compound used in the first step. Further,the lithium compound used in the third step may be the same as thelithium compound used in the first step or may be different from thelithium compound used in the first step.

In the third step, the composition of the first fired product isanalyzed to grasp the mol % of Nb, Li, Na, and K in the first firedproduct, and then the alkali compounds are mixed with the first firedproduct based on the obtained results of the compositional analysis, toobtain the second firing raw material having a ratio ((Li+Na+K)/Nb) ofthe total number of moles of alkali metal elements to the number ofmoles of Nb of 0.995 to 1.005, preferably 0.997 to 1.003, in terms ofatoms and a difference of a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falling within ±0.010.That is, in the third step, the amount of alkali metal elements in thesecond firing raw material is set to a molar ratio thereof to Nb of1.000±0.005, so as to be almost equimolar to Nb. Further, in the thirdstep, the ratio of the amounts of Na and K in the second firing rawmaterial is made equivalent to the molar ratio of Na and K in the alkaliniobate compound as a production object. When the alkali niobatecompound as a production object is an alkali niobate compound containinglithium, a lithium compound as an alkali compound is mixed with thefirst firing raw material in the first step, and lithium atoms are shortas compared with those in the alkali niobate compound as a productionobject, a lithium compound is mixed with the second firing raw materialin the third step in an amount corresponding to the shortage of lithiumatoms. Meanwhile, when the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, and a lithiumcompound as an alkali compound is not mixed with the first firing rawmaterial in the first step, a lithium compound is mixed with the secondfiring raw material in the third step in such a way as to give thecontent of lithium atoms in the alkali niobate compound as a productionobject.

In the third step, the sodium compound, the potassium compound, and thefirst fired product, and further the lithium compound, if desired, aredry-mixed. The dry-mixing method is not particularly limited, andexamples thereof include mixing methods using a blender, a ribbon mixer,a Henschel mixer, a food mixer, a super mixer, a Nauta mixer, a Juliamixer, or the like.

The fourth step is a step of firing the second firing raw materialobtained by performing the third step, to obtain an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.460 to 0.495,preferably 0.465 to 0.495, particularly preferably 0.470 to 0.490, interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005, preferably 0.997 to 1.003, in terms of atoms.

The ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the alkali niobate compoundobtained by performing the fourth step is preferably 0 or more and lessthan 0.10 in terms of atoms. When the molar ratio (Li/(Li+Na+K)) is 0,that is, when a sodium compound and a potassium compound are used asalkali compounds, the alkali niobate compound to be obtained ispotassium sodium niobate. When the molar ratio (Li/(Li+Na+K)) is morethan 0, that is, when a lithium compound, a sodium compound, and apotassium compound are used in combination as alkali compounds, thealkali niobate compound to be obtained is lithium potassium sodiumniobate.

In the fourth step, the firing temperature when firing the second firingraw material is 500 to 1000° C., preferably 550 to 900° C. Further, inthe fourth step, the firing time when firing the second firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the fourth step is performed to obtain the fired product, theobtained fired product may be ground, as required. For grinding thefired product, grinding devices such as a jet mill, a ball mill, a beadmill, an ultimizer, an atomizer, a nanomizer, a pulverizer, and a pinmill can be used.

The alkali niobate compound obtained by performing the fourth step maybe further fired at preferably 500 to 1000° C., particularly preferably700 to 900° C., for the purpose of enhancing the crystallinity. Further,the firing temperature at this time is appropriately selected, and ispreferably 3 to 20 hours, particularly preferably 5 to 15 hours. Thefiring atmosphere is an oxidizing atmosphere such as oxygen gas and air.

The alkali niobate compound obtained through firing may be ground, asrequired. For grinding the alkali niobate compound, grinding devicessuch as a jet mill, a ball mill, a bead mill, an ultimizer, an atomizer,a nanomizer, a pulverizer, and a pin mill can be used.

Thus, alkali niobate compound particles having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.460 to 0.495, preferably 0.465 to 0.495, particularlypreferably 0.470 to 0.490, in terms of atoms and a ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005, preferably 0.997 to 1.003, in termsof atoms can be obtained by the method for producing an alkali niobatecompound according to the present invention.

Thus, the method for producing alkali niobate compound particlesaccording to the present invention is performed to obtain alkali niobatecompound particles having a ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium of 0.460to 0.495, preferably 0.465 to 0.495, particularly preferably 0.470 to0.490, in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total numberof moles of alkali metal elements to the number of moles of niobium of0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms, that is,the piezoelectric material filler of the present invention.

The alkali niobate compound particles according to the present inventionthus obtained may be subjected to surface treatment in order to improvevarious properties such as water resistance, stability, anddispersibility, as long as their properties are not impaired. For thesurface treatment, surface-treating agents such as silane, titanate,aluminate, and zirconate coupling agents, fatty acids, fatty acidesters, higher alcohols, and hardened oils can be used.

The surface treatment method is not particularly limited, and thesurface treatment can be carried out using known methods. Examples ofthe surface treatment method include a wet method in which surfacetreatment is performed by dispersing the alkali niobate compoundparticles according to the present invention and a surface-treatingagent in water or an organic solvent, followed by filtration and drying.Further, examples of the surface treatment method include a dry methodin which surface treatment is performed by adding a surface-treatingagent to the alkali niobate compound particles according to the presentinvention by spraying or dripping, during the step of treating thealkali niobate compound particles with mixing/grinding devices such as aHenschel mixer, a ball mill, and a jet mill, followed by drying,heating, or the like.

The piezoelectric material filler of the present invention is suitablyused also as a production raw material for piezoelectric ceramicsproduced by sintering ceramic raw materials, and a filler for electretmaterials whose use as electrostatic induction conversion devices isproposed, other than the composite piezoelectric material of the presentinvention, which will be described below.

The composite piezoelectric material of the present invention comprisesa polymer matrix; and a piezoelectric material filler dispersed in thepolymer matrix, wherein the piezoelectric material filler comprisesalkali niobate compound particles having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.460 to 0.495 in terms of atoms and a ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005 in terms of atoms.

The composite piezoelectric material of the present invention comprisesa polymer matrix that serves as a base material in which a filler iscontained and dispersed, and a piezoelectric material filler dispersedin the polymer matrix.

The polymer matrix according to the composite piezoelectric material ofthe present invention is a synthetic resin or rubber. Examples of thesynthetic resin include thermosetting resins and thermoplastic resins.Examples of the thermosetting resins include epoxy resins such asbisphenol A and other epoxy resins, phenolic resins such as phenolformaldehyde resins, polyimide resins (PI), melamine resins, cyanateresins, bismaleimides, addition polymers of bismaleimides and diamines,polyfunctional cyanate ester resins, double-bond-added polyphenyleneoxide resins, unsaturated polyester resins, polyvinyl benzyl etherresins, polybutadiene resins, and fumarate resins. Examples of thethermoplastic resins include acrylic resins such aspolymethylmethacrylate, hydroxystyrene resins, phenolic resins such asnovolak, polyester resins such as polyethylene terephthalate, polyimideresins (TPI), polylactic acid resins, nylon resins, polyetherimideresins, silicone resins, ABS resins, and fluororesins such aspolyvinylidene fluoride. Examples of the rubber include natural rubbers,and synthetic rubbers such as isoprene rubber, butadiene rubber, styrenebutadiene rubber, chloroprene rubber, nitrile rubber, ethylene propylenerubber, acrylic rubber, fluororubber, epichlorohydrin rubber, urethanerubber, and silicone rubber.

The piezoelectric material filler according to the compositepiezoelectric material of the present invention comprises alkali niobatecompound particles having a ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium of 0.460to 0.495, preferably 0.465 to 0.495, particularly preferably 0.470 to0.490, in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total numberof moles of alkali metal elements to the number of moles of niobium of0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms. That is,the piezoelectric material filler according to the compositepiezoelectric material of the present invention is the piezoelectricmaterial filler of the present invention. Accordingly, the piezoelectricmaterial filler according to the composite piezoelectric material of thepresent invention is the same as the piezoelectric material filler ofthe present invention.

The piezoelectric material filler according to the compositepiezoelectric material of the present invention essentially containssodium and potassium as alkali compounds, and the compositepiezoelectric material filler according to the composite piezoelectricmaterial of the present invention may contain lithium for controllingthe variation of piezoelectric properties. As the composition ratio oflithium in the composite piezoelectric material filler, the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the total number ofmoles of alkali metal elements is 0 or more and less than 0.10,preferably 0 or more and less than 0.09, in terms of atoms, forachieving the aforementioned purposes.

In the composite piezoelectric material of the present invention, thecontent of the alkali niobate compound particles, that is, the contentof the piezoelectric material filler of the present invention is 20 to80 vol %, preferably 40 to 60 vol %, based on the entire compositepiezoelectric material.

The composite piezoelectric material of the present invention maycontain electrically conductive materials such as nickel particles,carbon black particles, and resin particles with their surfaces platedwith nickel or gold, other than the piezoelectric material filler of thepresent invention, within a range in which sufficient insulatingproperties as a composite piezoelectric body are maintained. Further,curing agents, glass powder, coupling agents, polymer additives,reactivity diluents, polymerization inhibitors, leveling agents,wettability improvers, surfactants, plasticizers, ultraviolet absorbers,antioxidants, inorganic fillers, antifungal agents, moisture controlagents, dye dissolving agents, buffers, chelating agents, flameretardants, silane coupling agents, and the like may be contained in arange that does not affect main electrical properties. Further, commonsolvents and the like may be used for adjusting the process suitability,as required. Examples of the solvents include alcohols such as tolueneand ethanol, ketones such as methyl ethyl ketone, and cycloalkanes suchas cyclohexane.

The form of the composite piezoelectric material of the presentinvention is not particularly limited, and examples thereof includevarious forms such as sheet, film, plate, porous, membrane, and fibrousforms, and laminated layers having an internal electrode structure. Theform is appropriately selected therefrom corresponding to the usage ofthe composite piezoelectric material.

The method for producing the composite piezoelectric material of thepresent invention is not particularly limited. For example, in the caseof producing the composite piezoelectric material of the presentinvention in the form of a sheet, a method for producing the compositepiezoelectric material of the present invention in the form of a sheetby first mixing the piezoelectric material filler of the presentinvention and a curing accelerator into a thermosetting resin, followedby kneading and dispersion, to obtain a resin paste, then forming theobtained resin paste into a sheet on a substrate by printing or thelike, and then heating the resin paste formed into a sheet together withthe substrate for thermosetting can be mentioned. In addition, examplesthereof include a method for producing the composite piezoelectricmaterial of the present invention in a desired shape by mixing thepiezoelectric material filler of the present invention into athermoplastic resin for mixing and dispersion by heating and melting,followed by injection molding using a mold. In addition, examplesthereof include a method for producing the composite piezoelectricmaterial of the present invention in the form of a sheet by mixing thepiezoelectric material filler of the present invention and avulcanization accelerator into a rubber substrate, followed by kneadingand dispersion, to obtain a rubber raw material mixture, then formingthe obtained rubber raw material mixture into a sheet on a substrate,and then heating the rubber raw material mixture formed into a sheettogether with the substrate for vulcanization. Electrodes are formedusing an existing suitable technique such as printing, vapor deposition,or the like, in the sheet composite material obtained by such a methodand, further appropriately polarization is performed using a coronadischarge system or the like, and thereby a composite piezoelectricdevice can be obtained exceptionally conveniently.

The composite piezoelectric device of the present invention is thecomposite piezoelectric material of the present invention formed into ashape corresponding to the form of use, that is, a compositepiezoelectric material comprising the piezoelectric material filler ofthe present invention and a polymer matrix, in which electrode formationand polarization are performed by suitable methods. That is, thecomposite piezoelectric device of the present invention is a compositepiezoelectric device having the composite piezoelectric material of thepresent invention subjected to polarization operation by a suitablepolarization method.

The composite piezoelectric device of the present invention can besuitably used for various sensors such as pressure sensors, pressuredistribution sensors, gyro sensors, shock sensors, seat sensors, andwearable sensors; damping materials used in precision electronics,automobiles, and buildings; power generating devices using environmentalvibration generated by human walking, driving of automobiles, or thelike; ignition devices such as lighters and gas appliances; oscillationcircuits used in receiving machines such as radios and televisions;various actuators used in driving devices of scanning probe microscopesor ultrasonic motors, and droplet discharge heads of inkjet printers;and medical materials relating to tissue reproduction.

In production of conventional alkali niobate compounds, when alkalicompounds and a niobium compound are mixed and fired, the alkalicompounds deliquesce, thereby making uniform mixing difficult, andtherefore the molar ratio of alkali metals in the composite metal oxideobtained by firing deviates from a desired molar ratio, and preciseadjustment of the molar ratio of alkali metals has been difficult.

Therefore, in the application research of the piezoelectric ceramics andpiezoelectric particles of conventional alkali niobate compounds,attempts to achieve excellent piezoelectric properties have been made bymixing potassium niobate containing 100 mol % of potassium, sodiumniobate containing 100 mol % of sodium, and lithium niobate containing100 mol % of lithium, as alkali metals, while adjusting the blendingratio of each compound so that desired piezoelectric properties can beobtained, using potassium sodium niobate with a molar ratio of sodiumand potassium of about 50 mol %:50 mol %, or further using the potassiumsodium niobate and lithium niobate in combination. However, sufficientresults could not have been obtained.

In contrast, in the method for producing alkali niobate compoundparticles according to the piezoelectric material filler of the presentinvention, after the molar ratio of Na and K is first adjusted to adesired molar ratio in the first step and the second step, and the ratioof the total number of moles of Li, Na, and K to the number of moles ofNb is set to 0.900 to 1.000, so that the total amount of Li, Na, and Kis equivalent to or slightly smaller than that of Nb, followed byfiring, to obtain a fired product, the molar ratio of Li, Na, K, and Nbis adjusted in the third step and the fourth step, to obtain a firedproduct. Therefore, the composition of the alkali niobate compound canbe precisely adjusted.

Thereby, the influence on piezoelectric properties by the difference inthe precise composition, which could not have been studiedconventionally, can be grasped in the present invention. The inventorshave found that, when the ratio of the number of moles of K to the totalnumber of moles of Na and K in the alkali niobate compound is 0.460 to0.495, preferably 0.465 to 0.495, particularly preferably 0.470 to0.490, excellent piezoelectric properties as a piezoelectric materialfiller are exhibited.

Next, a second invention of the present invention will be described.

<Second Invention>

A composite piezoelectric material of a first embodiment of the presentinvention (which will be hereinafter referred to also as the compositepiezoelectric material (1) of the present invention) comprises: apolymer matrix; and a composite piezoelectric material filler dispersedin the polymer matrix, wherein the composite piezoelectric materialfiller comprises: a small-particle size filler comprising an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium of 0.40to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total numberof moles of alkali metal elements to the number of moles of niobium of0.995 to 1.005 in terms of atoms; and a large-particle size fillercomprising an alkali niobate compound having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005 in terms of atoms, the total contentof the small-particle size filler and the large-particle size filler is20 to 80 vol % based on the entire composite piezoelectric material, thesmall-particle size filler has an average particle size (D50) of 0.1 to1.2 μm, the large-particle size filler has an average particle size(D50) of 1 to 15 μm, and the content ratio (large-particle sizefiller:small-particle size filler) of the large-particle size filler tothe small-particle size filler is 10:90 to 90:10 by volume.

The composite piezoelectric material (1) of the present inventioncomprises a polymer matrix that serves as a base material in which afiller is contained and dispersed, and a composite piezoelectricmaterial filler dispersed in the polymer matrix.

The polymer matrix according to the composite piezoelectric material (1)of the present invention is a synthetic resin or rubber. Examples of thesynthetic resin include thermosetting resins and thermoplastic resins.Examples of the thermosetting resins include epoxy resins such asbisphenol A and other epoxy resins, phenolic resins such as phenolformaldehyde resins, polyimide resins (PI), melamine resins, cyanateresins, bismaleimides, addition polymers of bismaleimides and diamines,polyfunctional cyanate ester resins, double-bond-added polyphenyleneoxide resins, unsaturated polyester resins, polyvinyl benzyl etherresins, polybutadiene resins, and fumarate resins. Examples of thethermoplastic resins include acrylic resins such aspolymethylmethacrylate, hydroxystyrene resins, phenolic resins such asnovolak, polyester resins such as polyethylene terephthalate, polyimideresins (TPI), polylactic acid resins, nylon resins, polyetherimideresins, silicone resins, ABS resins, and fluororesins such aspolyvinylidene fluoride. Examples of the rubber include natural rubbers,and synthetic rubbers such as isoprene rubber, butadiene rubber, styrenebutadiene rubber, chloroprene rubber, nitrile rubber, ethylene propylenerubber, acrylic rubber, fluororubber, epichlorohydrin rubber, urethanerubber, and silicon rubber.

The composite piezoelectric material (1) of the present inventioncomprises a small-particle size filler and a large-particle size filleras a composite piezoelectric material filler.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material (1) of the presentinvention are both particles of alkali niobate compounds. In thesmall-particle size filler and the large-particle size filler accordingto the composite piezoelectric material (1) of the present invention,the ratio (K/(Na+K)) of the number of moles of potassium to the totalnumber of moles of sodium and potassium is 0.40 to 0.60, preferably 0.45to 0.55, in terms of atoms. The ratio (K/(Na+K)) of the number of molesof potassium to the total number of moles of sodium and potassiumfalling within the aforementioned ranges enhances the piezoelectricproperties of the composite piezoelectric body. Further, in thesmall-particle size filler and the large-particle size filler accordingto the composite piezoelectric material (1) of the present invention,the ratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium is 0.995 to 1.005, preferably0.997 to 1.003, in terms of atoms. The small-particle size filler andthe large-particle size filler may have completely the same compositionwhile satisfying the aforementioned compositions, or the composition ofthe small-particle size filler and the composition of the large-particlesize filler may be different from each other within the range satisfyingthe aforementioned compositions.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material (1) of the presentinvention essentially contain sodium and potassium as alkali compoundsand may contain lithium for purposes such as improving the sinterabilityand controlling the variation of piezoelectric properties. In thecomposition ratio of lithium in each of the small-particle size fillerand the large-particle size filler, the ratio (Li/(Li+Na+K)) of thenumber of moles of lithium to the total number of moles of alkali metalelements is 0 or more and less than 0.10, preferably 0 or more and lessthan 0.09, in terms of atoms, in order not to impair the piezoelectricproperties while achieving the aforementioned purposes.

The alkali niobate compounds constituting the small-particle size fillerand the large-particle size filler according to the compositepiezoelectric material (1) of the present invention are perovskitealkali niobate compounds represented by the following general formula(1):

ANbO₃  (1).

In the alkali niobate compounds represented by the general formula (1),A essentially contains sodium and potassium and may contain lithium, theratio (K/(Na+K)) of the number of moles of potassium to the total numberof moles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to0.55, in terms of atoms, and the ratio ((Li+Na+K)/Nb) of the totalnumber of moles of alkali metal elements to the number of moles ofniobium is 0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms.

The average particle size (D50) of the small-particle size filler is 0.1to 1.2 μm, preferably 0.2 to 1.1 μm. Further, the average particle size(D50) of the large-particle size filler is 1 to 15 μm, preferably 2 to12 μm. The average particle sizes of the small-particle size filler andthe large-particle size filler falling within the aforementioned rangesenhances the piezoelectric properties of the composite piezoelectricmaterial. In the present invention, the average particle size is acumulative particle size at 50% (D50) determined in a volume frequencyparticle size distribution measurement measured by laser lightscattering using MT-3300EXII, manufactured by MicrotracBEL Corp.

The SPAN ((D90−D10)/D50) of the small-particle size filler is preferably0.2 to 2, particularly preferably 0.3 to 1.5. Further, the SPAN((D90−D10)/D50) of the large-particle size filler is preferably 0.3 to3, particularly preferably 0.4 to 2. The SPAN of the small-particle sizefiller and the SPAN of the large-particle size filler falling within theaforementioned ranges enhances the piezoelectric properties of thecomposite piezoelectric material. In the present invention, D10, D50,and D90 are cumulative particle sizes at 10%, 50%, and 90% determined ina volume frequency particle size distribution measurement measured bylaser light scattering using MT-3300EXII, manufactured by MicrotracBELCorp.

The average particle size (D50) of the small-particle size filler issmaller than the average particle size (D50) of the large-particle sizefiller, and the ratio (large-particle size filler/small-particle sizefiller) of the average particle size (D50) of the large-particle sizefiller to the average particle size (D50) of the small-particle sizefiller is preferably 2 to 150, particularly preferably 3 to 30. Theratio of the average particle size (D50) of the large-particle sizefiller to the average particle size (D50) of the small-particle sizefiller falling within the aforementioned ranges enhances thepiezoelectric properties of the composite piezoelectric material.

The BET specific surface area of the small-particle size filler ispreferably 2 to 15 m²/g, particularly preferably 2.5 to 10 m²/g.Further, the BET specific surface area of the large-particle size filleris preferably 0.1 to 3 m²/g, particularly preferably 0.2 to 2 m²/g.

In the composite piezoelectric material (1) of the present invention,the total content of the small-particle size filler comprising alkaliniobate compound particles and the large-particle size filler comprisingan alkali niobate compound is 20 to 80 vol %, preferably 40 to 60 vol %,based on the entire composite piezoelectric material.

In the composite piezoelectric material (1) of the present invention,the content ratio (large-particle size filler:small-particle sizefiller) of the large-particle size filler to the small-particle sizefiller is 10:90 to 90:10, preferably 20:80 to 80:20, by volume.

The composite piezoelectric material (1) of the present invention hasimproved compositeness with resins and, furthermore enhancedpiezoelectric properties, as compared with fillers not combining asmall-particle size filler and a large-particle size filler, bycontaining a small-particle size filler having a predetermined averageparticle size and a large-particle size filler having a predeterminedaverage particle size at predetermined volume fractions to combine thesmall-particle size filler and the large-particle size filler.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material of the presentinvention are suitably produced by the method for producing an alkaliniobate compound according to the present invention shown below.

The method for producing an alkali niobate compound according to thepresent invention is a method for producing an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.40 to 0.60 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, the method comprising: a first step ofdry-mixing alkali compounds and a niobium compound in an amount giving aratio ((Li+Na+K)/Nb) of the number of moles of alkali metal elements tothe number of moles of Nb of 0.900 to 1.000 in terms of atoms and adifference of a ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K from the ratio of the number of molesof K to the total number of moles of Na and K in the alkali niobatecompound as a production object falling within ±0.015, to prepare afirst firing raw material; a second step of firing the first firing rawmaterial at 500 to 750° C., to obtain a first fired product; a thirdstep of dry-mixing alkali compounds with the first fired product in anamount giving a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of Nb of 0.995 to 1.005 interms of atoms and a difference of a ratio (K/(Na+K)) of the number ofmoles of K to the total number of moles of Na and K from the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the alkali niobate compound as a production object fallingwithin ±0.010, to prepare a second firing raw material; and a fourthstep of firing the second firing raw material at 500 to 1000° C., toobtain the alkali niobate compound.

The first step is a step of dry-mixing alkali compounds and a niobiumcompound, to prepare a first firing raw material. The alkali compoundsaccording to the first step essentially contain both a sodium compoundand a potassium compound and may contain a lithium compound.

The sodium compound according to the first step is a compound having asodium atom, and examples thereof include sodium carbonate, sodiumhydrogencarbonate, sodium hydroxide, sodium oxalate, and sodiumtartrate. The sodium compound may be of one type or a combination of twoor more types. As the sodium compound, sodium carbonate (Na₂CO₃) ispreferable for good handleability and good reactivity. Further, a higherpurity of the sodium compound is preferable.

The average particle size (D50) of the sodium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the sodium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the sodium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the sodiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The potassium compound according to the first step is a compound havinga potassium atom, and examples thereof include potassium carbonate,potassium hydrogencarbonate, potassium hydroxide, potassium oxalate, andpotassium tartrate. The potassium compound may be of one type or acombination of two or more types. As the potassium compound, potassiumcarbonate (K₂CO₃) is preferable for good handleability and goodreactivity throughout blending to firing. Further, a higher purity ofthe potassium compound is preferable.

The average particle size (D50) of the potassium compound according tothe first step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the potassium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the potassium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the potassiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The lithium compound according to the first step is a compound having alithium atom, and examples thereof include lithium carbonate, sodiumhydrogencarbonate, lithium hydroxide, lithium oxalate, and lithiumtartrate. The lithium compound may be of one type or a combination oftwo or more types. As the lithium compound, lithium carbonate (Li₂CO₃)is preferable for good handleability and good reactivity. Further, ahigher purity of the lithium compound is preferable.

The average particle size (D50) of the lithium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the lithium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the lithium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the lithiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The niobium compound according to the first step is a compound having aniobium atom, and examples thereof include niobium pentoxide, niobiumhydroxide, and ammonium niobium oxalate. The niobium compound may be ofone type or a combination of two or more types. As the niobium compound,niobium pentoxide (Nb₂O₅) is preferable for easy handleability and goodprecision composition control. Further, a higher purity of the niobiumcompound is preferable.

The average particle size (D50) of the niobium compound according to thefirst step is not particularly limited, and is preferably 0.1 to 15 μm,particularly preferably 0.2 to 12 μm. The average particle size (D50) ofthe niobium compound falling within the aforementioned ranges increasesthe mixability with other raw materials and facilitates the adjustmentof the composition, thereby enabling effective reaction in firing, whichwill be described below. Further, the BET specific surface area of theniobium compound according to the first step is not particularlylimited, and is preferably 0.1 to 15 m²/g, particularly preferably 0.2to 10 m²/g. The BET specific surface area of the niobium compoundfalling within the aforementioned ranges enables production of an alkaliniobate compound having excellent dispersibility and good crystallinityeven in the dry method. The average particle size in the presentinvention is a cumulative particle size at 50% (D50) determined in avolume frequency particle size distribution measurement measured bylaser light scattering using MT3300EXII, manufactured by MicrotracBELCorp.

In the first step, the first firing raw material is obtained bydry-mixing the alkali compounds and the niobium compound in an amountgiving a ratio ((Li+Na+K)/Nb) of the total number of moles of alkalimetal elements to the number of moles of Nb of 0.900 to 1.000,preferably 0.920 to 0.995, in terms of atoms and a difference of a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K from the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the alkali niobate compound as aproduction object falling within ±0.015. That is, in the first step, theamount of the alkali metal elements in the first firing raw material ismade equimolar to Nb or slightly less than the equimolar amount to Nb.Further, in the first step, the ratio of the amounts of Na and K in thefirst firing raw material is made equivalent to the molar ratio of Naand K in the alkali niobate compound as a production object. The alkaliniobate compound as a production object is an alkali niobate compoundthat is intended to be obtained by performing the method for producingan alkali niobate compound according to the present invention. When thealkali niobate compound as a production object is an alkali niobatecompound containing lithium, a lithium compound as an alkali compoundmay be mixed or not mixed to the first firing raw material in the firststep, as long as the ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of Nb is 0.900 to 1.000,preferably 0.920 to 0.995, in terms of atoms. When the alkali niobatecompound as a production object is an alkali niobate compound containinglithium, a lithium compound as an alkali compound is mixed with thefirst firing raw material in the first step, and lithium atoms are shortas compared with those in the alkali niobate compound as a productionobject, a lithium compound is mixed with the second firing raw materialin the third step in an amount corresponding to the shortage of lithiumatoms. Meanwhile, when the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, and a lithiumcompound as an alkali compound is not mixed with the first firing rawmaterial in the first step, a lithium compound is mixed with the secondfiring raw material in the third step in such a way as to give thecontent of lithium atoms in the alkali niobate compound as a productionobject.

In the present invention, the phrase, the difference of the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the first firing raw material from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falls within ±0.015,means that, when the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the first firing raw material interms of atoms is referred to as Y, and the ratio (K/(Na+K)) of thenumber of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object is referred to as Z, thevalue “Y−Z” falls within ±0.015. For example, when producing an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K of 0.45, the ratio (K/(Na+K))of the number of moles of K to the total number of moles of Na and K inthe first firing raw material is set to a molar ratio of 0.435 to 0.465in terms of atoms. Further, the same applies to the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thesecond firing raw material, which will be described below.

In the first step, alkali compounds and a niobium compound aredry-mixed. The dry-mixing method is not particularly limited, andexamples thereof include mixing methods using a blender, a ribbon mixer,a Henschel mixer, a food mixer, a super mixer, a Nauta mixer, a Juliamixer, or the like.

The second step is a step of firing the first firing raw materialobtained by performing the first step, to obtain a first fired product.

In the second step, the firing temperature when firing the first firingraw material is 500 to 750° C., preferably 550 to 700° C. Further, inthe second step, the firing time when firing the first firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the second step is performed to obtain the first fired product,the obtained first fired product may be ground, as required. Forgrinding the first fired product, grinding devices such as a jet mill, aball mill, a bead mill, an ultimizer, an atomizer, a nanomizer, apulverizer, and a pin mill can be used.

The third step is a step of dry-mixing alkali compounds with the firstfired product obtained by performing the second step, to prepare asecond firing raw material.

The alkali compounds according to the third step are the same as thealkali compounds according to the first step. The sodium compound usedin the third step may be the same as the sodium compound used in thefirst step or may be different from the sodium compound used in thefirst step. Further, the potassium compound used in the third step maybe the same as the potassium compound used in the first step or may bedifferent from the potassium compound used in the first step. Further,the lithium compound used in the third step may be the same as thelithium compound used in the first step or may be different from thelithium compound used in the first step.

In the third step, the composition of the first fired product isanalyzed to grasp the mol % of Nb, Li, Na, and K in the first firedproduct, and then the alkali compounds are mixed with the first firedproduct based on the obtained results of the compositional analysis, toobtain the second firing raw material having a ratio ((Li+Na+K)/Nb) ofthe total number of moles of alkali metal elements to the number ofmoles of Nb of 0.995 to 1.005, preferably 0.997 to 1.003, in terms ofatoms and a difference of a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falling within ±0.010.That is, in the third step, the amount of alkali metal elements in thesecond firing raw material is set to a molar ratio thereof to Nb of1.000±0.005, so as to be almost equimolar to Nb. Further, in the thirdstep, the ratio of the amounts of Na and K in the second firing rawmaterial is made equivalent to the molar ratio of Na and K in the alkaliniobate compound as a production object. When the alkali niobatecompound as a production object is an alkali niobate compound containinglithium, a lithium compound as an alkali compound is mixed with thefirst firing raw material in the first step, and lithium atoms are shortas compared with those in the alkali niobate compound as a productionobject, a lithium compound is mixed with the second firing raw materialin the third step in an amount corresponding to the shortage of lithiumatoms. Meanwhile, when the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, and a lithiumcompound as an alkali compound is not mixed with the first firing rawmaterial in the first step, a lithium compound is mixed with the secondfiring raw material in the third step in such a way as to give thecontent of lithium atoms in the alkali niobate compound as a productionobject.

In the third step, the sodium compound, the potassium compound, and thefirst fired product, and further the lithium compound, if desired, aredry-mixed. The dry-mixing method is not particularly limited, andexamples thereof include mixing methods using a blender, a ribbon mixer,a Henschel mixer, a food mixer, a super mixer, a Nauta mixer, a Juliamixer, or the like.

The fourth step is a step of firing the second firing raw materialobtained by performing the third step, to obtain an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60,preferably 0.45 to 0.55, in terms of atoms and a ratio ((Li+Na+K)/Nb) ofthe total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005, preferably 0.997 to 1.003, in termsof atoms.

In the alkali niobate compound obtained by performing the fourth step,the ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements is preferably 0 or more andless than 0.10 in terms of atoms. When the molar ratio (Li/(Li+Na+K)) is0, that is, when a sodium compound and a potassium compound are used asalkali compounds, the alkali niobate compound to be obtained ispotassium sodium niobate. When the molar ratio (Li/(Li+Na+K)) is morethan 0, that is, when a lithium compound, a sodium compound, and apotassium compound are used in combination as alkali compounds, thealkali niobate compound to be obtained is lithium potassium sodiumniobate.

In the fourth step, the firing temperature when firing the second firingraw material is 500 to 1000° C., preferably 550 to 900° C. Further, inthe fourth step, the firing time when firing the second firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the fourth step is performed to obtain the fired product, theobtained fired product may be ground, as required. For grinding thefired product, grinding devices such as a jet mill, a ball mill, a beadmill, an ultimizer, an atomizer, a nanomizer, a pulverizer, and a pinmill can be used.

The alkali niobate compound obtained by performing the fourth step maybe further fired at preferably 500 to 1000° C., particularly preferably700 to 900° C., for the purpose of enhancing the crystallinity. Further,the firing temperature at this time is appropriately selected, and ispreferably 3 to 20 hours, particularly preferably 5 to 15 hours. Thefiring atmosphere is an oxidizing atmosphere such as oxygen gas and air.

The alkali niobate compound obtained after firing may be ground, asrequired. For grinding the alkali niobate compound, grinding devicessuch as a jet mill, a ball mill, a bead mill, an ultimizer, an atomizer,a nanomizer, a pulverizer, and a pin mill can be used.

Thus, alkali niobate compound particles having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.40 to 0.60, preferably 0.45 to 0.55, in terms of atomsand a ratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium of 0.995 to 1.005, preferably0.997 to 1.003, in terms of atoms can be obtained by the method forproducing an alkali niobate compound according to the present invention.The particle sizes of niobium compounds serving as raw materials areappropriately managed by preliminary adjustment such as grinding andclassification, so that alkali niobate compound particles for thesmall-particle size filler and alkali niobate compound particles for thelarge-particle size filler are produced separately. That is, in themethod for producing alkali niobate compound particles according to thepresent invention, alkali niobate compound particles for thesmall-particle size filler and alkali niobate compound particles for thelarge-particle size filler can be produced separately, for example, byperforming an operation such as grinding or classification after thesecond step is performed, so that the particle sizes of the firedproduct are adjusted to the particle size range of the small-particlesize filler or the particle size range of the large-particle sizefiller, performing an operation such as grinding or classification afterthe fourth step is performed, so that the particle sizes of the firedproduct are adjusted to the particle size range of the small-particlesize filler or the particle size range of the large-particle sizefiller, or adjusting the firing time in the second step or the firingtime in the fourth step.

The alkali niobate compound particles according to the present inventionthus obtained may be subjected to surface treatment in order to improvevarious properties such as water resistance, stability, anddispersibility, as long as their properties are not impaired. For thesurface treatment, surface-treating agents such as silane, titanate,aluminate, and zirconate coupling agents, fatty acids, fatty acidesters, higher alcohols, and hardened oils can be used.

The surface treatment method is not particularly limited, and thesurface treatment can be carried out using known methods. Examples ofthe surface treatment method include a wet method in which surfacetreatment is performed by dispersing the alkali niobate compoundparticles according to the present invention and a surface-treatingagent in water or an organic solvent, followed by filtration and drying.Further, examples of the surface treatment method include a dry methodin which surface treatment is performed by adding a surface-treatingagent to the alkali niobate compound particles according to the presentinvention by spraying or dripping, while the alkali niobate compoundparticles are being processed with mixing/grinding devices such as aHenschel mixer, a ball mill, and a jet mill, followed by drying,heating, or the like.

The composite piezoelectric material (1) of the present invention maycontain electrically conductive materials such as nickel particles,carbon black particles, and resin particles with their surfaces platedwith nickel or gold, other than the small-particle size filler and thelarge-particle size filler according to the composite piezoelectricmaterial (1) of the present invention, within a range in whichsufficient insulating properties as a composite piezoelectric body aremaintained. Further, curing agents, glass powder, coupling agents,polymer additives, reactivity diluents, polymerization inhibitors,leveling agents, wettability improvers, surfactants, plasticizers,ultraviolet absorbers, antioxidants, inorganic fillers, antifungalagents, moisture control agents, dye dissolving agents, buffers,chelating agents, flame retardants, silane coupling agents, and the likemay be contained in a range that does not affect main electricalproperties. Further, common solvents and the like may be used foradjusting the process suitability, as required. Examples of the solventsinclude alcohols such as toluene and ethanol, ketones such as methylethyl ketone, and cycloalkanes such as cyclohexane.

A composite piezoelectric material of a second embodiment of the presentinvention (which will be hereinafter referred to also as the compositepiezoelectric material (2) of the present invention) comprises: apolymer matrix; and a composite piezoelectric material filler dispersedin the polymer matrix, wherein the composite piezoelectric materialfiller comprises an alkali niobate compound having a ratio (K/(Na+K)) ofthe number of moles of potassium to the total number of moles of sodiumand potassium of 0.40 to 0.60 in terms of atoms and a ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of niobium of 0.995 to 1.005 in terms of atoms, thecontent of the alkali niobate compound is 20 to 80 vol % based on theentire composite piezoelectric material, and the alkali niobate compoundexhibits a bimodal particle size distribution including a first peakhaving a peak top in a particle size range of 0.1 to 1.0 μm and a secondpeak having a peak top in a particle size range of 1 to 15 μm in aparticle size distribution measurement, wherein a ratio (B/A) of a value(B) of a frequency (%) of the particle size at the peak top of thesecond peak to a value (A) of a frequency (%) of the particle size atthe peak top of the first peak is 0.1 to 20.

The composite piezoelectric material (2) of the present inventioncomprises a polymer matrix that serves as a base material in which afiller is contained and dispersed, and a composite piezoelectricmaterial filler dispersed in the polymer matrix.

The polymer matrix according to the composite piezoelectric material (2)of the present invention is a synthetic resin or rubber. The polymermatrix according to the composite piezoelectric material (2) of thepresent invention is the same as the polymer matrix according to thecomposite piezoelectric material (1) of the present invention.

The composite piezoelectric material filler according to the compositepiezoelectric material (2) of the present invention is particles of analkali niobate compound. The composite piezoelectric material filleraccording to the composite piezoelectric material (2) of the presentinvention is the same as in the method for producing the small-particlesize filler and the large-particle size filler according to thecomposite piezoelectric material (1) of the present invention. That is,the composite piezoelectric material filler according to the compositepiezoelectric material (2) of the present invention is suitably producedby the method for producing an alkali niobate compound according to thepresent invention.

In the composite piezoelectric material filler according to thecomposite piezoelectric material (2) of the present invention, the ratio(K/(Na+K)) of the number of moles of potassium to the total number ofmoles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to 0.55,in terms of atoms. The ratio (K/(Na+K)) of the number of moles ofpotassium to the number of moles of sodium and potassium falling withinthe aforementioned ranges enhances the piezoelectric properties of thecomposite piezoelectric material. Further, in the compositepiezoelectric material filler according to the composite piezoelectricmaterial (2) of the present invention, the ratio ((Li+Na+K)/Nb) of thetotal number of moles of alkali metal elements to the number of moles ofniobium is 0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms.

The composite piezoelectric material filler according to the compositepiezoelectric material (2) of the present invention essentially containssodium and potassium as alkali compounds, and the compositepiezoelectric material filler according to the composite piezoelectricmaterial (2) of the present invention may contain lithium for purposessuch as improving the sinterability and controlling the variation ofpiezoelectric properties. In the composition ratio of lithium in thealkali niobate compound particles, the ratio (Li/(Li+Na+K)) of thenumber of moles of lithium to the total number of moles of alkali metalelements is 0 or more and less than 0.10, preferably 0 or more and lessthan 0.09, in terms of atoms, in order not to impair the piezoelectricproperties while achieving the aforementioned purposes.

The alkali niobate compound constituting the composite piezoelectricmaterial filler according to the composite piezoelectric material (2) ofthe present invention is a perovskite alkali niobate compoundrepresented by the following general formula (1):

ANbO₃  (1).

In the alkali niobate compound represented by the general formula (1), Aessentially contains sodium and potassium and may contain lithium, theratio (K/(Na+K)) of the number of moles of potassium to the total numberof moles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to0.55, in terms of atoms, and the ratio ((Li+Na+K)/Nb) of the totalnumber of moles of alkali metal elements to the number of moles ofniobium is 0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms.

The alkali niobate compound in the composite piezoelectric material (2)of the present invention exhibits a bimodal particle size distributionincluding a first peak having a peak top in a particle size range of 0.1to 1.2 μm, preferably 0.2 to 1.1 μm and a second peak having a peak topin a particle size range of 1 to 15 μm, preferably 2 to 12 μm, in aparticle size distribution measurement. In the present invention, theparticle size distribution measurement is a volume frequency particlesize distribution measurement measured by laser light scattering usingMT-3300EXII, manufactured by MicrotracBEL Corp., and the first peak andthe second peak indicate peaks in a particle size distribution chartobtained by such a volume particle size distribution measurement.

The ratio (B/A) of the value (B) of the frequency (%) of the particlesize at the peak top of the second peak to the value (A) of thefrequency (%) of the particle size at the peak top of the first peak is0.1 to 20, preferably 0.2 to 18, particularly preferably 0.3 to 15, inthe particle size distribution measurement of the alkali niobatecompound in the composite piezoelectric material (2) of the presentinvention. The value B/A in the particle size distribution measurementof the alkali niobate compound in the composite piezoelectric material(2) of the present invention falling within the aforementioned rangesimproves the dispersibility of the alkali niobate compound in thepolymer matrix and, further enhances the piezoelectric properties of thecomposite piezoelectric material to be obtained.

In the particle size distribution measurement of the alkali niobatecompound in the composite piezoelectric material (2) of the presentinvention, the particle size at the peak top of the first peak issmaller than the particle size at the peak top of the second peak, and aratio (the particle size at the peak top of the second peak/the particlesize at the peak top of the first peak) of the particle size at the peaktop of the second peak to the particle size at the peak top of the firstpeak is preferably 2 to 150, particularly preferably 3 to 30. The ratio(the particle size at the peak top of the second peak/the particle sizeat the peak top of the first peak) of the particle size at the peak topof the second peak to the particle size at the peak top of the firstpeak falling within the aforementioned ranges enhances the piezoelectricproperties of the composite piezoelectric material.

In the composite piezoelectric material (2) of the present invention,the content of the alkali niobate compound is 20 to 80 vol %, preferably40 to 60 vol %, based on the entire composite piezoelectric material.

The composite piezoelectric material (2) of the present invention hasenhanced piezoelectric properties by containing particles of the bimodalalkali niobate compound having a predetermined size distribution.

The forms of the composite piezoelectric material (1) of the presentinvention and the composite piezoelectric material (2) of the presentinvention are not particularly limited, and examples thereof includevarious forms such as sheet, film, plate, porous, membrane, and fibrousforms, and laminated layers having an internal electrode structure. Theforms are appropriately selected therefrom corresponding to the usage ofthe composite piezoelectric material.

The method for producing the composite piezoelectric material (1) of thepresent invention or the composite piezoelectric material (2) of thepresent invention is not particularly limited. For example, in the caseof producing the composite piezoelectric material (1) of the presentinvention or the composite piezoelectric material (2) of the presentinvention in the form of a sheet, a method for producing the compositepiezoelectric material (1) of the present invention or the compositepiezoelectric material (2) of the present invention in the form of asheet by first mixing the composite piezoelectric material filleraccording to the composite piezoelectric material of the presentinvention and a curing accelerator into a thermosetting resin, followedby kneading and dispersion, to obtain a resin paste, then forming theobtained resin paste into a sheet on a substrate by printing or thelike, and then heating the resin paste formed into a sheet together withthe substrate for thermosetting can be mentioned. In addition, examplesthereof include a method for producing the composite piezoelectricmaterial (1) of the present invention or the composite piezoelectricmaterial (2) of the present invention in a desired shape by mixing thecomposite piezoelectric material filler according to the compositepiezoelectric material of the present invention into a thermoplasticresin for mixing and dispersion by heating and melting, followed byinjection molding using a mold. In addition, examples thereof include amethod for producing the composite piezoelectric material (1) of thepresent invention or the composite piezoelectric material (2) of thepresent invention in the form of a sheet by mixing the compositepiezoelectric material filler according to the composite piezoelectricmaterial of the present invention and a vulcanization accelerator into arubber substrate, followed by kneading and dispersion, to obtain arubber raw material mixture, then forming the obtained rubber rawmaterial mixture into a sheet on a substrate, and then heating therubber raw material mixture formed into a sheet together with thesubstrate for vulcanization. Electrodes are formed using an existingsuitable technique such as printing, vapor deposition, or the like, inthe sheet composite material obtained by such a method and, furtherappropriately polarization is performed using a corona discharge systemor the like, and thereby a composite piezoelectric device can beobtained exceptionally conveniently.

The composite piezoelectric device of the present invention is thecomposite piezoelectric material (1) of the present invention formedinto a shape corresponding to the form of use, that is, a compositepiezoelectric material comprising the composite piezoelectric materialfiller of the first embodiment of the present invention described belowand a polymer matrix, or the composite piezoelectric material (2) of thepresent invention formed into a shape corresponding to the form of use,that is, a composite piezoelectric material comprising the compositepiezoelectric material filler of the second embodiment of the presentinvention described below and a polymer matrix, in which electrodeformation and polarization are performed by suitable methods. That is,the composite piezoelectric device of the present invention is acomposite piezoelectric device having the composite piezoelectricmaterial (1) of the present invention subjected to polarizationoperation or the composite piezoelectric material (2) of the presentinvention subjected to polarization operation.

The composite piezoelectric device of the present invention can besuitably used for various sensors such as pressure sensors, pressuredistribution sensors, gyro sensors, shock sensors, seat sensors, andwearable sensors; damping materials used in precision electronics,automobiles, and buildings; power generating devices using environmentalvibration generated by human walking, driving of automobiles, or thelike; ignition devices such as lighters and gas appliances; oscillationcircuits used in receiving machines such as radios and televisions;various actuators used in driving devices of scanning probe microscopesor ultrasonic motors, and droplet discharge heads of inkjet printers;and medical materials relating to tissue reproduction.

The composite piezoelectric material filler of the first embodiment ofthe present invention (which will be hereinafter referred to also as thecomposite piezoelectric material filler (1) of the present invention) isa mixture of a small-particle size filler comprising an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60 interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms and a large-particle size filler comprising analkali niobate compound having a ratio (K/(Na+K)) of the number of molesof potassium to the total number of moles of sodium and potassium of0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of the totalnumber of moles of alkali metal elements to the number of moles ofniobium of 0.995 to 1.005 in terms of atoms, wherein the small-particlesize filler has an average particle size (D50) of 0.1 to 1.2 μm, thelarge-particle size filler has an average particle size (D50) of 1 to 15μm, and a mixing ratio (large-particle size filler:small-particle sizefiller) of the large-particle size filler to the small-particle sizefiller is 10:90 to 90:10 by volume.

The composite piezoelectric material filler (1) of the present inventionis a filler for a composite piezoelectric material used for producing acomposite piezoelectric material comprising a polymer matrix and afiller by being contained and dispersed in the polymer matrix.

The composite piezoelectric material filler (1) of the present inventionis a mixture of a small-particle size filler and a large-particle sizefiller.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention are the same as the small-particle size filler and thelarge-particle size filler according to the composite piezoelectricmaterial (1) of the present invention. That is, the small-particle sizefiller and the large-particle size filler according to the compositepiezoelectric material filler (1) of the present invention are bothparticles of alkali niobate compounds. In the small-particle size fillerand the large-particle size filler according to the compositepiezoelectric material filler (1) of the present invention, the ratio(K/(Na+K)) of the number of moles of potassium to the total number ofmoles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to 0.55,in terms of atoms. The ratio (K/(Na+K)) of the number of moles ofpotassium to the number of moles of sodium and potassium falling withinthe aforementioned ranges enhances the piezoelectric properties of thecomposite piezoelectric material. Further, in the small-particle sizefiller and the large-particle size filler according to the compositepiezoelectric material filler (1) of the present invention, the ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of niobium is 0.995 to 1.005, preferably 0.997 to1.003, in terms of atoms. The small-particle size filler and thelarge-particle size filler may have completely the same compositionwhile satisfying the aforementioned compositions, or the composition ofthe small-particle size filler and the composition of the large-particlesize filler may be different from each other within the range satisfyingthe aforementioned compositions.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention essentially contain sodium and potassium as alkalicompounds, but the small-particle size filler and the large-particlesize filler according to the composite piezoelectric material filler (1)of the present invention may contain lithium, for purposes such asimproving the sinterability and controlling the variation ofpiezoelectric properties. In the composition ratio of lithium in thesmall-particle size filler and the large-particle size filler, the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the total number ofmoles of alkali metal elements is 0 or more and less than 0.10,preferably 0 or more and less than 0.09, in terms of atoms, in order notto impair the piezoelectric properties while achieving theaforementioned purposes.

The alkali niobate compounds constituting the small-particle size fillerand the large-particle size filler according to the compositepiezoelectric material filler (1) of the present invention areperovskite alkali niobate compounds represented by the following generalformula (1):

ANbO₃  (1).

In the alkali niobate compounds represented by the general formula (1),A essentially contains sodium and potassium and may contain lithium, theratio (K/(Na+K)) of the number of moles of potassium to the total numberof moles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to0.55, in terms of atoms, and the ratio ((Li+Na+K)/Nb) of the totalnumber of moles of alkali metal elements to the number of moles ofniobium is 0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms.

The average particle size (D50) of the small-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention is 0.1 to 1.2 μm, preferably 0.2 to 1.1 μm. Further,the average particle size (D50) of the large-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention is 1 to 15 μm, preferably 2 to 12 μm. The averageparticle sizes of the small-particle size filler and the large-particlesize filler falling within the aforementioned ranges enhances thepiezoelectric properties of the composite piezoelectric material. In thepresent invention, the average particle size is a cumulative particlesize at 50% (D50) determined in a volume frequency particle sizedistribution measurement measured by laser light scattering usingMT-3300EXII, manufactured by MicrotracBEL Corp.

The SPAN ((D90−D10)/D50) of the small-particle size filler according tothe composite piezoelectric material filler (1) of the present inventionis preferably 0.2 to 2, particularly preferably 0.3 to 1.5. Further, theSPAN ((D90−D10)/D50) of the large-particle size filler is preferably 0.3to 3, particularly preferably 0.4 to 2. The SPAN of the small-particlesize filler and the SPAN of the large-particle size filler fallingwithin the aforementioned ranges enhances the piezoelectric propertiesof the composite piezoelectric material. In the present invention, D10,D50, and D90 are cumulative particle sizes at 10%, 50%, and 90%determined in a volume frequency particle size distribution measurementmeasured by laser light scattering using MT-3300EXII, manufactured byMicrotracBEL Corp.

The average particle size (D50) of the small-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention is smaller than the average particle size (D50) of thelarge-particle size filler, and the ratio (large-particle sizefiller/small-particle size filler) of the average particle size (D50) ofthe large-particle size filler to the average particle size (D50) of thesmall-particle size filler is preferably 2 to 150, particularlypreferably 3 to 30. The ratio of the average particle size (D50) of thelarge-particle size filler to the average particle size (D50) of thesmall-particle size filler falling within the aforementioned rangesenhances the piezoelectric properties of the composite piezoelectricmaterial.

The BET specific surface area of the small-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention is preferably 2 to 15 m²/g, particularly preferably2.5 to 10 m²/g. Further, the BET specific surface area of thelarge-particle size filler according to the composite piezoelectricmaterial filler (1) of the present invention is preferably 0.1 to 3m²/g, particularly preferably 0.2 to 2 m²/g.

In the composite piezoelectric material filler (1) of the presentinvention, the content ratio (large-particle size filler:small-particlesize filler) of the large-particle size filler to the small-particlesize filler is 10:90 to 90:10, preferably 20:80 to 80:20, by volume.

The composite piezoelectric material filler (1) of the present inventionhas enhanced piezoelectric properties, as compared with fillers notcombining a small-particle size filler and a large-particle size filler,by containing a small-particle size filler having a predeterminedaverage particle size and a large-particle size filler having apredetermined average particle size at predetermined volume fractions tocombine the small-particle size filler and the large-particle sizefiller.

The small-particle size filler and the large-particle size filleraccording to the composite piezoelectric material filler (1) of thepresent invention are suitably produced by the method for producingalkali niobate compound particles according to the present inventiondescribed above. The small-particle size filler and the large-particlesize filler obtained by the method for producing alkali niobate compoundparticles of the present invention are mixed at predetermined volumefractions, and thereby a mixture in which the small-particle size fillerand the large-particle size filler are mixed at predetermined fractions,that is, the composite piezoelectric material filler (1) of the presentinvention can be obtained.

The composite piezoelectric material filler of the second embodiment ofthe present invention (which will be hereinafter referred to also as thecomposite piezoelectric material filler (2) of the present invention)comprises an alkali niobate compound having a ratio (K/(Na+K)) of thenumber of moles of potassium to the total number of moles of sodium andpotassium of 0.40 to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of niobium of 0.995 to 1.005 in terms of atoms, the compositepiezoelectric material filler exhibiting a bimodal particle sizedistribution including a first peak having a peak top in a particle sizerange of 0.1 to 1.2 μm and a second peak having a peak top in a particlesize range of 1 to 15 μm in a particle size distribution measurement,wherein a ratio (B/A) of a value (B) of a frequency (%) of the particlesize at the peak top of the second peak to a value (A) of a frequency(%) of the particle size at the peak top of the first peak is 0.1 to 20.

The composite piezoelectric material filler (2) of the present inventionis a filler for a composite piezoelectric material used for producing acomposite piezoelectric material comprising a polymer matrix and afiller by being contained and dispersed in the polymer matrix.

The composite piezoelectric material filler (2) of the present inventionis the same as the composite piezoelectric material filler according tothe composite piezoelectric material (2) of the present invention. Thatis, the composite piezoelectric material filler (2) of the presentinvention is particles of an alkali niobate compound. In the compositepiezoelectric material filler (2) of the present invention, the ratio(K/(Na+K)) of the number of moles of potassium to the total number ofmoles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to 0.55,in terms of atoms. The ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium fallingwithin the aforementioned ranges enhances the piezoelectric propertiesof the composite piezoelectric material. Further, in the compositepiezoelectric material filler (2) of the present invention, the ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of niobium is 0.995 to 1.005, preferably 0.997 to1.003, in terms of atoms.

The potassium sodium niobate constituting the composite piezoelectricmaterial filler (2) of the present invention is a perovskite alkaliniobate compound represented by the following general formula (1):

$\begin{matrix}{{ANb}{O_{3}.}} & (1)\end{matrix}$

In the alkali niobate compound represented by the general formula (1), Aessentially contains sodium and potassium and may contain lithium, theratio (K/(Na+K)) of the number of moles of potassium to the total numberof moles of sodium and potassium is 0.40 to 0.60, preferably 0.45 to0.55, in terms of atoms, and the ratio ((Li+Na+K)/Nb) of the totalnumber of moles of alkali metal elements to the number of moles ofniobium is 0.995 to 1.005, preferably 0.997 to 1.003, in terms of atoms.

The composite piezoelectric material filler (2) of the present inventionexhibits a bimodal particle size distribution including a first peakhaving a peak top in a particle size range of 0.1 to 1.2 μm, preferably0.2 to 1.1 μm, and a second peak having a peak top in a particle sizerange of 1 to 15 μm, preferably 2 to 12 μm, in a particle sizedistribution measurement. In the present invention, the particle sizedistribution measurement is a volume frequency particle sizedistribution measurement measured by laser light scattering usingMT-3300EXII, manufactured by MicrotracBEL Corp., and the first peak andthe second peak indicate peaks in a particle size distribution chartobtained by such a volume particle size distribution measurement.

The ratio (B/A) of the value (B) of the frequency (%) of the particlesize at the peak top of the second peak to the value (A) of thefrequency (%) of the particle size at the peak top of the first peak is0.1 to 20, preferably 0.2 to 18, particularly preferably 0.3 to 15, inthe particle size distribution measurement of the compositepiezoelectric material filler (2) of the present invention. The valueB/A in the particle size distribution measurement of the alkali niobatecompound in the composite piezoelectric material (2) of the presentinvention falling within the aforementioned ranges improves thedispersibility of the alkali niobate compound in the polymer matrix and,further enhances the piezoelectric properties of the compositepiezoelectric material to be obtained.

In the particle size distribution measurement of the compositepiezoelectric material filler (2) of the present invention, the particlesize at the peak top of the first peak is smaller than the particle sizeat the peak top of the second peak, and a ratio (the particle size atthe peak top of the second peak/the particle size at the peak top of thefirst peak) of the particle size at the peak top of the second peak tothe particle size at the peak top of the first peak is preferably 2 to150, particularly preferably 3 to 30. The ratio (the particle size atthe peak top of the second peak/the particle size at the peak top of thefirst peak) of the particle size at the peak top of the second peak tothe particle size at the peak top of the first peak falling within theaforementioned ranges enhances the piezoelectric properties of thecomposite piezoelectric material.

The composite piezoelectric material filler (2) of the present inventionis bimodal particles having a predetermined particle size distribution,thereby having enhanced piezoelectric properties of the compositepiezoelectric material.

As the method for producing the composite piezoelectric material filler(2) of the present invention, the composite piezoelectric materialfiller (2) of the present invention can be obtained, for example, byproducing a small-particle size filler having a particle sizedistribution of the first peak and a large-particle size filler having aparticle size distribution of the second peak by the aforementionedmethod for producing an alkali niobate compound of the presentinvention, and mixing them in such a way as to give a predeterminedparticle size distribution.

A composite piezoelectric material filler of a third embodiment of thepresent invention is a composite piezoelectric material filler used forthe composite piezoelectric material (1) of the present invention, thecomposite piezoelectric material filler comprising an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60 interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, and the composite piezoelectric material fillerhaving an average particle size (D50) of 0.1 to 1.2 μm. That is, thecomposite piezoelectric material filler of the third embodiment of thepresent invention is a composite piezoelectric material filler used asthe small-particle size filler in the composite piezoelectric material(1) of the present invention.

The composite piezoelectric material filler of the third embodiment ofthe present invention is the same as the small-particle size filleraccording to the composite piezoelectric material (1) of the presentinvention.

A composite piezoelectric material filler of a fourth embodiment of thepresent invention is a composite piezoelectric material filler used forthe composite piezoelectric material (1) of the present invention, thecomposite piezoelectric material filler comprising an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60 interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, and the composite piezoelectric material fillerhaving an average particle size (D50) of 1 to 15 μm. That is, thecomposite piezoelectric material filler of the fourth embodiment of thepresent invention is a composite piezoelectric material filler used asthe large-particle size filler in the composite piezoelectric material(1) of the present invention.

The composite piezoelectric material filler of the fourth embodiment ofthe present invention is the same as the large-particle size filleraccording to the composite piezoelectric material (1) of the presentinvention.

Composite piezoelectric materials can be obtained by separatelydispersing the composite piezoelectric material filler of the thirdembodiment of the present invention and the composite piezoelectricmaterial filler of the fourth embodiment of the present inventionrespectively in polymer matrices, and examples of the form of useinclude various forms such as sheet, film, plate, porous, membrane, andfibrous forms, and laminated layers having an internal electrodestructure. The form is appropriately selected therefrom corresponding tothe usage of the composite piezoelectric material. For example, in thecase of producing a composite piezoelectric material in the form of asheet, a method for producing the composite piezoelectric material inthe form of a sheet by first simultaneously or separately kneading athermosetting resin with the composite piezoelectric material filler ofthe third embodiment of the present invention and the compositepiezoelectric material filler of the fourth embodiment of the presentinvention, further mixing a curing accelerator therewith, followed bykneading and dispersion, to obtain a resin paste, then forming theobtained resin paste into a sheet on a substrate by printing or thelike, and then heating the resin paste formed into a sheet together withthe substrate for thermosetting can be mentioned. In addition, examplesthereof include a method for producing a composite piezoelectricmaterial in a desired shape by simultaneously or separately kneading athermoplastic resin with the composite piezoelectric material filler ofthe third embodiment of the present invention and the compositepiezoelectric material filler of the fourth embodiment of the presentinvention for mixing and dispersion by heating and melting, followed byinjection molding using a mold. In addition, examples thereof include amethod for producing a composite piezoelectric material in the form of asheet by simultaneously or separately kneading a rubber substrate withthe composite piezoelectric material filler of the third embodiment ofthe present invention and the composite piezoelectric material filler ofthe fourth embodiment of the present invention, further mixing avulcanization accelerator therewith, followed by kneading anddispersion, to obtain a rubber raw material mixture, then forming theobtained rubber raw material mixture into a sheet on a substrate, andthen heating the rubber raw material mixture formed into a sheettogether with the substrate for vulcanization. Electrodes are formedusing an existing suitable technique such as printing, vapor deposition,or the like, in the sheet composite material obtained by such a methodand, further appropriately polarization is performed using a coronadischarge system or the like, and thereby a composite piezoelectricdevice can be obtained exceptionally conveniently.

Next, a third invention of the present invention will be described.

<Third Invention>

The method for producing an alkali niobate compound according to thepresent invention is a method for producing an alkali niobate compoundhaving a ratio ((Li+Na+K)/Nb) of the total number of moles of alkalimetal elements to the number of moles of Nb of 0.995 to 1.005 in termsof atoms, the method comprising: a first step of dry-mixing alkalicompounds and a niobium compound in an amount giving a ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of Nb of 0.900 to 1.000 in terms of atoms and adifference of a ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K from the ratio (K/(Na+K)) of thenumber of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falling within ±0.015, toprepare a first firing raw material; a second step of firing the firstfiring raw material at 500 to 750° C., to obtain a first fired product;a third step of dry-mixing alkali compounds with the first fired productin an amount giving a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of Nb of 0.995 to 1.005in terms of atoms and a difference of a ratio (K/(Na+K)) of the numberof moles of K to the total number of moles of Na and K from a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the alkali niobate compound as a production object fallingwithin ±0.010, to prepare a second firing raw material; and a fourthstep of firing the second firing raw material at 500 to 1000° C., toobtain the alkali niobate compound.

The first step is a step of dry-mixing alkali compounds and a niobiumcompound, to prepare a first firing raw material. The alkali compoundsaccording to the first step are any of a lithium compound, a sodiumcompound, and a potassium compound, or a combination of any two or moreof a lithium compound, a sodium compound, and a potassium compound. Thatis, only a lithium compound, only a sodium compound, or only a potassiumcompound may be used as an alkali compound, or any two or more of alithium compound, a sodium compound, and a potassium compound may beused in combination as alkali compounds.

The lithium compound according to the first step is a compound having alithium atom, and examples thereof include lithium carbonate, sodiumhydrogencarbonate, lithium hydroxide, lithium oxalate, and lithiumtartrate. The lithium compound may be of one type or a combination oftwo or more types. As the lithium compound, lithium carbonate (Li₂CO₃)is preferable for good handleability and good reactivity. Further, ahigher purity of the lithium compound is preferable.

The average particle size (D50) of the lithium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the lithium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the lithium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the lithiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The sodium compound according to the first step is a compound having asodium atom, and examples thereof include sodium carbonate, sodiumhydrogencarbonate, sodium hydroxide, sodium oxalate, and sodiumtartrate. The sodium compound may be of one type or a combination of twoor more types. As the sodium compound, sodium carbonate (Na₂CO₃) ispreferable for good handleability and good reactivity. Further, a higherpurity of the sodium compound is preferable.

The average particle size (D50) of the sodium compound according to thefirst step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the sodium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the sodium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the sodiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The potassium compound according to the first step is a compound havinga potassium atom, and examples thereof include potassium carbonate,potassium hydrogencarbonate, potassium hydroxide, potassium oxalate, andpotassium tartrate. The potassium compound may be of one type or acombination of two or more types. As the potassium compound, potassiumcarbonate (K₂CO₃) is preferable for good handleability and goodreactivity throughout blending to firing. Further, a higher purity ofthe potassium compound is preferable.

The average particle size (D50) of the potassium compound according tothe first step is not particularly limited, and is preferably 1000 μm orless, particularly preferably 10 to 100 μm. The average particle size(D50) of the potassium compound falling within the aforementioned rangesincreases the mixability with other raw materials and facilitates theadjustment of the composition, thereby enabling effective reaction infiring, which will be described below. Further, the BET specific surfacearea of the potassium compound according to the first step is notparticularly limited, and is preferably 0.01 to 5 m²/g, particularlypreferably 0.1 to 3 m²/g. The BET specific surface area of the potassiumcompound falling within the aforementioned ranges increases themixability with other raw materials and facilitates the adjustment ofthe composition, thereby enabling effective reaction in firing, whichwill be described below.

The niobium compound according to the first step is a compound having aniobium atom, and examples thereof include niobium pentoxide, niobiumhydroxide, and ammonium niobium oxalate. The niobium compound may be ofone type or a combination of two or more types. As the niobium compound,niobium pentoxide (Nb₂O₅) is preferable for easy handleability and goodprecision composition control. Further, a higher purity of the niobiumcompound is preferable.

The average particle size (D50) of the niobium compound according to thefirst step is not particularly limited, and is preferably 0.1 to 15 μm,particularly preferably 0.2 to 12 μm. The average particle size (D50) ofthe niobium compound falling within the aforementioned ranges increasesthe mixability with other raw materials and facilitates the adjustmentof the composition, thereby enabling effective reaction in firing, whichwill be described below. Further, the BET specific surface area of theniobium compound according to the first step is not particularlylimited, and is preferably 0.1 to 15 m²/g, particularly preferably 0.2to 10 m²/g. The BET specific surface area of the niobium compoundfalling within the aforementioned ranges enables production of an alkaliniobate compound having excellent dispersibility and good crystallinityeven in the dry method. The average particle size in the presentinvention is a cumulative particle size at 50% (D50) determined in avolume frequency particle size distribution measurement measured bylaser light scattering using MT3300EXII, manufactured by MicrotracBELCorp.

In the first step, alkali compounds and a niobium compound are mixed inan amount giving a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of Nb of 0.900 to 1.000,preferably 0.920 to 0.995, in terms of atoms and a difference of a ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K from the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the alkali niobate compound as aproduction object falling within ±0.015, to obtain a first firing rawmaterial. That is, in the first step, the amount of the alkali metalelements in the first firing raw material is made equimolar to Nb orslightly less than the equimolar amount to Nb. Further, in the firststep, the ratio of the amounts of Na and K in the first firing rawmaterial is made equivalent to the molar ratio of Na and K in the alkaliniobate compound as a production object. The alkali niobate compound asa production object is an alkali niobate compound that is intended to beobtained by performing the method for producing an alkali niobatecompound of the present invention. When the alkali niobate compound as aproduction object is an alkali niobate compound containing lithium, alithium compound as an alkali compound may be mixed or not mixed to thefirst firing raw material in the first step, as long as the ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of Nb is 0.900 to 1.000, preferably 0.920 to 0.995,in terms of atoms. When the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, a lithiumcompound as an alkali compound is mixed with the first firing rawmaterial in the first step, and lithium atoms are short as compared withthose in the alkali niobate compound as a production object, a lithiumcompound is mixed with the second firing raw material in the third stepin an amount corresponding to the shortage of lithium atoms. Meanwhile,when the alkali niobate compound as a production object is an alkaliniobate compound containing lithium, and a lithium compound as an alkalicompound is not mixed with the first firing raw material in the firststep, a lithium compound is mixed with the second firing raw material inthe third step in such a way as to give the content of lithium atoms inthe alkali niobate compound as a production object.

In the present invention, the phrase, the difference of the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K in the first firing raw material from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falls within ±0.015,means that, when the ratio (K/(Na+K)) of the number of moles of K to thetotal number of moles of Na and K in the first firing raw material interms of atoms is referred to as Y, and the ratio (K/(Na+K)) of thenumber of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object is referred to as Z, thevalue “Y−Z” falls within ±0.015. For example, when producing an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K of 0.45, the ratio (K/(Na+K))of the number of moles of K to the total number of moles of Na and K inthe first firing raw material is set to a molar ratio of 0.435 to 0.465in terms of atoms. Further, the same applies to the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thesecond firing raw material, which will be described below.

In the first step, alkali compounds and a niobium compound aredry-mixed. The dry-mixing method is not particularly limited, andexamples thereof include mixing methods using a blender, a ribbon mixer,a Henschel mixer, a food mixer, a super mixer, a Nauta mixer, a Juliamixer, or the like.

The second step is a step of firing the first firing raw materialobtained by performing the first step, to obtain a first fired product.

In the second step, the firing temperature when firing the first firingraw material is 500 to 750° C., preferably 550 to 700° C. Further, inthe second step, the firing time when firing the first firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the second step is performed to obtain the first fired product,the obtained first fired product may be ground, as required. Forgrinding the first fired product, grinding devices such as a jet mill, aball mill, a bead mill, an ultimizer, an atomizer, a nanomizer, apulverizer, and a pin mill can be used.

The third step is a step of dry-mixing alkali compounds with the firstfired product obtained by performing the second step, to prepare asecond firing raw material.

The alkali compounds according to the third step are the same as thealkali compounds according to the first step. The lithium compound usedin the third step may be the same as the lithium compound used in thefirst step or may be a lithium compound that is different from thelithium compound used in the first step. The sodium compound used in thethird step may be the same as the sodium compound used in the first stepor may be a sodium compound that is different from the sodium compoundused in the first step. Further, the potassium compound used in thethird step may be the same as the potassium compound used in the firststep or may be a potassium compound that is different from the potassiumcompound used in the first step.

In the third step, the composition of the first fired product isanalyzed to grasp the mol % of Nb, Li, Na, and K in the first firedproduct, and then the alkali compounds are mixed with the first firedproduct based on the obtained results of the compositional analysis, toobtain the second firing raw material having a ratio ((Li+Na+K)/Nb) ofthe total number of moles of alkali metal elements to the number ofmoles of Nb of 0.995 to 1.005, preferably 0.997 to 1.003, in terms ofatoms and a difference of a ratio (K/(Na+K)) of the number of moles of Kto the total number of moles of Na and K from the ratio (K/(Na+K)) ofthe number of moles of K to the total number of moles of Na and K in thealkali niobate compound as a production object falling within ±0.010.That is, in the third step, the amount of alkali metal elements in thesecond firing raw material is set to a molar ratio thereof to Nb of1.000±0.005, so as to be almost equimolar to Nb. Further, in the thirdstep, the ratio of the amounts of Na and K in the second firing rawmaterial is made equivalent to the molar ratio of Na and K in the alkaliniobate compound as a production object. When the alkali niobatecompound as a production object is an alkali niobate compound containinglithium, a lithium compound as an alkali compound is mixed with thefirst firing raw material in the first step, and lithium atoms are shortas compared with those in the alkali niobate compound as a productionobject, a lithium compound is mixed with the second firing raw materialin the third step in an amount corresponding to the shortage of lithiumatoms. Meanwhile, when the alkali niobate compound as a productionobject is an alkali niobate compound containing lithium, and a lithiumcompound as an alkali compound is not mixed with the first firing rawmaterial in the first step, a lithium compound is mixed with the secondfiring raw material in the third step in such a way as to give thecontent of lithium atoms in the alkali niobate compound as a productionobject.

In the third step, a sodium compound, a potassium compound, and thefirst fired product are dry-mixed. The dry-mixing method is notparticularly limited, and examples thereof include mixing methods usinga blender, a ribbon mixer, a Henschel mixer, a food mixer, a supermixer, a Nauta mixer, a Julia mixer, or the like.

The fourth step is a step of firing the second firing raw materialobtained by performing the third step, to obtain an alkali niobatecompound.

In the alkali niobate compound obtained by performing the fourth step,the ratio (K/(Na+K)) of the number of moles of potassium to the totalnumber of moles of Na and K is preferably 0 to 1.000 in terms of atoms.When the molar ratio (K/(Na+K)) is 0, that is, when any of a lithiumcompound and a sodium compound or both of them are used as alkalicompounds, the alkali niobate compound to be obtained is lithiumniobate, sodium niobate, or lithium sodium niobate. Further, when themolar ratio (K/(Na+K)) is 1.000, that is, when any of a lithium compoundand a potassium compound or both of them are used as alkali compounds,the alkali niobate compound to be obtained is lithium niobate, potassiumniobate, or lithium potassium niobate. When the molar ratio (K/(Na+K))is more than 0 and less than 1.000, that is, when any two or more of alithium compound, a sodium compound, and a potassium compound are usedin combination as alkali compounds, the alkali niobate compound to beobtained is potassium sodium niobate or lithium potassium sodiumniobate.

In the alkali niobate compound obtained by performing the fourth step,the ratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements is preferably 0 to 0.100 interms of atoms. When the molar ratio (Li/(Li+Na+K)) is 0, that is, whenany of a sodium compound and a potassium compound or both of them areused as alkali compounds, the alkali niobate compound to be obtained issodium niobate, potassium niobate, or potassium sodium niobate. Further,when the molar ratio (Li/(Li+Na+K)) is more than 0, that is, when anytwo or more of a lithium compound, a sodium compound, and a potassiumcompound are used in combination as alkali compounds, the alkali niobatecompound to be obtained is lithium sodium niobate, lithium potassiumniobate, or lithium potassium sodium niobate.

In the alkali niobate compound obtained by performing the fourth step,the ratio ((Li+Na+K)/Nb) of the total number of moles of alkali metalelements to the number of moles of niobium is preferably 0.995 to 1.005,further preferably 0.997 to 1.003, in terms of atoms.

The alkali niobate compound obtained by performing the fourth step is aperovskite or ilmenite alkali niobate compound represented by thefollowing general formula (1):

$\begin{matrix}{{ANb}{O_{3}.}} & (1)\end{matrix}$

In the alkali niobate compound represented by the general formula (1), Ais at least one selected from lithium, sodium, and potassium, the ratio(K/(Na+K)) of the number of moles of K to the total number of moles ofNa and K is 0 to 1.000 in terms of atoms, the ratio (Li/(Li+Na+K)) ofthe number of moles of Li to the total number of moles of alkali metalelements is 0 to 0.100 in terms of atoms, and the ratio ((Li+Na+K)/Nb)of the total number of moles of alkali metal elements to the number ofmoles of Nb is 0.995 to 1.005, further preferably 0.997 to 1.003, interms of atoms.

In the fourth step, the firing temperature when firing the second firingraw material is 500 to 1000° C., preferably 550 to 900° C. Further, inthe fourth step, the firing time when firing the second firing rawmaterial is appropriately selected, and is preferably 3 to 20 hours,particularly preferably 5 to 15 hours, and the firing atmosphere is anoxidizing atmosphere such as oxygen gas and air.

After the fourth step is performed to obtain the fired product, theobtained fired product may be ground, as required. For grinding thefired product, grinding devices such as a jet mill, a ball mill, a beadmill, an ultimizer, an atomizer, a nanomizer, a pulverizer, and a pinmill can be used.

The alkali niobate compound obtained by performing the fourth step isfurther fired at preferably 500 to 1000° C., particularly preferably 700to 900° C., so that the crystallinity can be enhanced, or sintering canproceed, as desired. Further, the firing temperature at this time isappropriately selected, and is preferably 3 to 20 hours, particularlypreferably 5 to 15 hours. The firing atmosphere is an oxidizingatmosphere such as oxygen gas and air.

The alkali niobate compound obtained after firing may be ground, asrequired. For grinding the alkali niobate compound, grinding devicessuch as a jet mill, a ball mill, a bead mill, an ultimizer, an atomizer,a nanomizer, a pulverizer, and a pin mill can be used.

The average particle size (D50) of the alkali niobate compound thusobtained by performing the method for producing an alkali niobatecompound of the present invention is not particularly limited, and ispreferably 0.1 to 15 μm, particularly preferably 0.2 to 12 μm. Further,the BET specific surface area of the alkali niobate compound obtained byperforming the method for producing an alkali niobate compound of thepresent invention is not particularly limited, and is preferably 0.1 to15 m²/g, particularly preferably 0.2 to 10 m²/g.

The alkali niobate compound particles according to the present inventionobtained may be subjected to surface treatment in order to improvevarious properties such as water resistance, stability, anddispersibility as long as their properties are not impaired. For thesurface treatment, surface-treating agents such as silane, titanate,aluminate, and zirconate coupling agents, fatty acids, fatty acidesters, higher alcohols, and hardened oils can be used.

The surface treatment method is not particularly limited, and thesurface treatment can be carried out using known methods. Examples ofthe surface treatment method include a wet method in which surfacetreatment is performed by dispersing the alkali niobate compoundparticles according to the present invention and a surface-treatingagent in water or an organic solvent, followed by filtration and drying.Further, examples of the surface treatment method include a dry methodin which surface treatment is performed by adding a surface-treatingagent to the alkali niobate compound particles according to the presentinvention by spraying or dripping, while the alkali niobate compoundparticles are being processed with mixing/grinding devices such as aHenschel mixer, a ball mill, and a jet mill, followed by drying,heating, or the like.

The alkali niobate compound particles according to the present inventionthus obtained may be used in the form of paints such as pastes,slurries, and varnishes by being mixed with solvents. As the solventsused when the alkali niobate compound particles are used in the form ofpaints, common solvents in such a technical field are used, and examplesthereof include alcohols such as toluene and ethanol, ketones such asmethyl ethyl ketone, and cycloalkanes such as cyclohexane. Further,corresponding to the form of use, organic additives such as binders,various resin and rubber polymer materials that serve as base materialsfor forming composites, inorganic additives such as flux materials,dispersants or the like may be contained in the paints, as required.

The obtained paints are formed into products of fibrous, sheet, film,plate, and other shapes by existing forming techniques, so as to besuitably used for fabrication in various applications, which will bedescribed below.

The alkali niobate compound obtained by performing the method forproducing an alkali niobate compound of the present invention issuitably used as a production raw material for piezoelectric ceramicsproduced by sintering ceramic raw materials, a filler of a compositepiezoelectric material in which a composite piezoelectric materialfiller is dispersed in a polymer matrix, a filler for electret materialswhose use as electrostatic induction conversion devices is proposed,using the alkali niobate compound according to the present inventionitself as a raw material, other than the use in the form of paints.Further, it is suitably used as these applications as various sensorssuch as pressure sensors, pressure distribution sensors, gyro sensors,shock sensors, seat sensors, and wearable sensors; damping materialsused in precision electronics, automobiles, and buildings; powergenerating devices using environmental vibration generated by humanwalking, driving of automobiles, or the like; ignition devices such aslighters and gas appliances; oscillation circuits used in receivingmachines such as radios and televisions; various actuators used indriving devices of scanning probe microscopes or ultrasonic motors, anddroplet discharge heads of inkjet printers; and medical materialsrelating to tissue reproduction.

In conventional methods for producing an alkali niobate compound, whenalkali compounds and a niobium compound are mixed and fired, the alkalicompounds deliquesce, thereby making uniform mixing difficult, andtherefore the molar ratio of alkali metals in the composite metal oxideobtained by firing deviates from a desired molar ratio, and preciseadjustment of the molar ratio of alkali metals has been difficult.

In contrast, in the method for producing an alkali niobate compound ofthe present invention, after the molar ratio of Na and K is firstadjusted to a desired molar ratio in the first step and the second step,and the ratio of the total number of moles of alkali metal elements tothe number of moles of Nb is set to 0.900 to 1.000, so that the totalamount of alkali metal elements is equivalent to or slightly smallerthan Nb, followed by firing, to obtain a fired product, the molar ratioof alkali metal elements and Nb is adjusted in the third step and thefourth step, to obtain a fired product. Therefore, the composition ofthe alkali niobate compound can be precisely adjusted.

EXAMPLES

Hereinafter, the present invention will be described by way of examples,but the present invention is not limited to these examples.

Example 1 <Production of Potassium Sodium Niobate>

With the target composition of each element being set so that sodium was26.25 mol %, potassium was 23.75 mol %, niobium was 50.00 mol %, theratio ((Na+K)/Nb) of alkali metals to niobium was 1.000, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.475, 4485 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.),937 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1108 g of potassium carbonate (fine powder for foodadditives, K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were dry-mixedusing a Henschel mixer (FM-20B, manufactured by NIPPON COKE &ENGINEERING CO., LTD.) under conditions of 2000 rpm and 2.5 minutes, toobtain a first firing raw material.

The first firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd). After cooling to room temperature, it was groundusing a jet mill (STJ-200, manufactured by Seishin Enterprise Co., Ltd.)under conditions of a processing speed of 6 kg/h, an introductionpressure of 0.6 MPa, and a grinding pressure of 0.5 MPa, to obtain afirst ground product.

As a result of analyzing the composition of the first ground product byfluorescent X-ray, sodium was 26.47 mol %, potassium was 23.28 mol %,niobium was 50.25 mol %, the ratio ((Na+K)/Nb) of alkali metals toniobium was 0.990, and the ratio (K/(Na+K)) of potassium to the totalalkali metals was 0.468.

In order to finely adjust the ratio ((Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to the totalalkali metals to 0.475, 29 g of potassium carbonate was added to 5500 gof the first ground product, followed by dry-mixing using a Henschelmixer under conditions of 2000 rpm and 3 minutes, to obtain a secondfiring raw material.

The second firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace. After cooling to roomtemperature, it was ground using a jet mill under conditions of aprocessing speed of 10 kg/h, an introduction pressure of 0.6 MPa, and agrinding pressure of 0.5 MPa, to obtain a second ground product.

As a result of analyzing the composition of the second ground product byfluorescent X-ray, sodium was 26.36 mol %, potassium was 23.68 mol %,niobium was 49.96 mol %, the ratio ((Na+K)/Nb) of alkali metals toniobium was 1.002, and the ratio (K/(Na+K)) of potassium to the totalalkali metals was 0.473.

In order to further enhance the crystallization, the second groundproduct was fired at 900° C. for 15 hours using an elevating electricfurnace. After cooling to room temperature, it was ground using a jetmill under conditions of a processing speed of 5 kg/h, an introductionpressure of 0.30 MPa, and a grinding pressure of 0.15 MPa, to obtainpotassium sodium niobate particles.

<Analysis>

As a result of analyzing the composition of the obtained potassiumsodium niobate by fluorescent X-ray using ZSX100e, manufactured byRigaku Corporation, the ratio ((Na+K)/Nb) of alkali metals to niobiumwas 1.001, and the ratio (K/(Na+K)) of potassium to the total alkalimetals was 0.473.

Further, the obtained potassium sodium niobate was subjected to X-raydiffraction analysis (XRD) using UltimaIV, manufactured by RigakuCorporation, and scanning electron microscopy (SEM) using S-4800,manufactured by Hitachi High-Technologies Corporation. The results areshown in FIG. 1 and FIG. 2.

From the XRD chart of FIG. 1, it was confirmed that the obtainedpotassium sodium niobate was in a single phase.

Further, the particle size distribution of the obtained potassium sodiumniobate was measured using MT-3300EXII, manufactured by MicrotracBELCorp. As a result, the average particle size D50 was 0.68 μm.

Further, the BET specific surface area of the obtained potassium sodiumniobate was measured using Macsorb HM model-1208, manufactured byMountech Co., Ltd. As a result, the BET specific surface area was 4.61m²/g.

<Fabrication of Composite Piezoelectric Material and CompositePiezoelectric Device>

The potassium sodium niobate particles obtained in Example 1 werekneaded with an epoxy resin at a fraction of 40 vol %, to obtain anepoxy resin composition. The epoxy resin used herein was composed of 99mass % of a thermosetting epoxy resin (product name: JER® 828EL,manufactured by Mitsubishi Chemical Corporation, with a molecular weightof about 370, a specific gravity of 1.17, and a nominal viscosity at 25°C. of 120 to 150P), and 1 mass % of an imidazole curing accelerator(product name: 2E4MZ, manufactured by SHIKOKU CHEMICALS CORPORATION).The obtained epoxy resin composition was cured at 140° C. for 5 hours tofabricate a plate composite piezoelectric material with a thickness of0.6 mm. Subsequently, 30-nm thick platinum films were formed aselectrodes on both surfaces of the obtained composite piezoelectricmaterial by vapor deposition, and thereafter −8.0 kV was applied theretousing a corona discharge system (ELC-01N, manufactured by ELEMENT Co.,Ltd.) for 30 minutes, to obtain a composite piezoelectric devicepolarized in the thickness direction.

The piezoelectric constant (d₃₃), the relative permittivity, and thedielectric loss of the composite piezoelectric device obtained inExample 1 were measured by the following measurement methods. As aresult, the piezoelectric constant (d₃₃) was 0.55 pC/N, the relativepermittivity was 23.1, and the dielectric loss was 0.006. Further, thepiezoelectric constant (g₃₃) determined from the piezoelectric constant(d₃₃) and the relative permittivity was 2.7×10⁻³ V·m/N.

(Measurement Method)

<Piezoelectric Constant (d₃₃)>

The composite piezoelectric device was set in the force head of apiezometer system (PM200, manufactured by Piezo Test Ltd.) in thethickness direction, and the static force was adjusted to 5 N. The d₃₃was measured with a vibration frequency of 110 Hz and a force of 0.25 N.

<Relative Permittivity and Dielectric Loss>

Using an impedance analyzer (1255B, manufactured by SolartronAnalytical) and an interface (1296, manufactured by SolartronAnalytical), the relative permittivity and the dielectric loss at afrequency of 100 Hz and an applied voltage of 1 V were measured.

Example 2

The same procedure as in Example 1 was performed except that the targetcomposition of each element was changed so that sodium was 25.5 mol %,and potassium was 24.5 mol %, instead of sodium being 26.25 mol %, andpotassium being 23.75 mol %.

As a result, the ratio ((Na+K)/Nb) of alkali metals to niobium was1.000, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.489, in the obtained potassium sodium niobate. Other variousproperties are shown in Table 1. Further, it was confirmed from the XRDchart that the obtained potassium sodium niobate was in a single phase.

After a composite piezoelectric device was obtained from the obtainedpotassium sodium niobate by the same method as in Example 1, theelectrical properties were measured. As a result, the piezoelectricconstant (d₃₃) was 0.56 pC/N, the relative permittivity was 22.4, andthe dielectric loss was 0.007. Further, the piezoelectric constant (g₃₃)determined from the piezoelectric constant (d₃₃) and the relativepermittivity was 2.8×10⁻³ V·m/N.

Comparative Example 1

The same procedure as in Example 1 was performed except that the targetcomposition of each element was changed so that sodium was 25.00 mol %,potassium was 25.00 mol %, and the ratio (K/(Na+K)) of potassium to thetotal alkali metals was 0.500, instead of sodium being 26.25 mol %,potassium being 23.75 mol %, and the ratio (K/(Na+K)) of potassium tothe total alkali metals being 0.475.

As a result, the ratio ((Na+K)/Nb) of alkali metals to niobium was0.999, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.498, in the obtained potassium sodium niobate. Other variousproperties are shown in Table 1. Further, it was confirmed from the XRDchart that the obtained potassium sodium niobate was in a single phase.

After a composite piezoelectric device was obtained from the obtainedpotassium sodium niobate by the same method as in Example 1, theelectrical properties were measured. As a result, the piezoelectricconstant (d₃₃) was 0.26 pC/N, the relative permittivity was 22.0, andthe dielectric loss was 0.007. Further, the piezoelectric constant (g₃₃)determined from the piezoelectric constant (d₃₃) and the relativepermittivity was 1.3×10⁻³ V·m/N.

Comparative Example 2

The same procedure as in Example 1 was performed except that the targetcomposition of each element was changed so that sodium was 27.50 mol %,potassium was 22.50 mol %, and the ratio (K/(Na+K)) of potassium to thetotal alkali metals was 0.450, instead of sodium being 26.25 mol %,potassium being 23.75 mol %, and the ratio (K/(Na+K)) of potassium tothe total alkali metals being 0.475.

As a result, the ratio ((Na+K)/Nb) of alkali metals to niobium was0.999, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.448, in the obtained potassium sodium niobate. Other variousproperties are shown in Table 1. Further, it was confirmed from the XRDchart that the obtained potassium sodium niobate was in a single phase.

After a composite piezoelectric device was obtained from the obtainedpotassium sodium niobate by the same method as in Example 1, theelectrical properties were measured. As a result, the piezoelectricconstant (d₃₃) was 0.30 pC/N, the relative permittivity was 22.3, andthe dielectric loss was 0.007. Further, the piezoelectric constant (g₃₃)determined from the piezoelectric constant (d₃₃) and the relativepermittivity was 1.5×10⁻³ V·m/N.

Comparative Example 3

The same procedure as in Example 1 was performed except that the targetcomposition of each element was changed so that sodium was 28.75 mol %,potassium was 21.25 mol %, and the ratio (K/(Na+K)) of potassium to thetotal alkali metals was 0.425, instead of sodium being 26.25 mol %,potassium being 23.75 mol %, and the ratio (K/(Na+K)) of potassium tothe total alkali metals being 0.475.

As a result, the ratio ((Na+K)/Nb) of alkali metals to niobium was1.001, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.424, in the obtained potassium sodium niobate. Other variousproperties are shown in Table 1. Further, it was confirmed from the XRDchart that the obtained potassium sodium niobate was in a single phase.

After a composite piezoelectric device was obtained from the obtainedpotassium sodium niobate by the same method as in Example 1, theelectrical properties were measured. As a result, the piezoelectricconstant (d₃₃) was 0.12 pC/N, the relative permittivity was 22.8, andthe dielectric loss was 0.007. Further, the piezoelectric constant (g₃₃)determined from the piezoelectric constant (d₃₃) and the relativepermittivity was 0.6×10⁻³ V·m/N.

TABLE 1 Comparative Comparative Comparative Example 1 Example 2 Example1 Example 2 Example 3 Composite piezoelectric material filler (K +Na)/Nb Molar ratio 1.001 1.000 0.999 0.999 1.001 K/(K + Na) Molar ratio0.473 0.489 0.498 0.448 0.423 Average particle size (D50) μm 0.68 0.670.67 0.67 0.68 BET specific surface area m³/g 4.61 4.66 4.65 4.76 4.74Composite piezoelectric device Piezoelectric constant d₃₃ pC/N 0.55 0.560.26 0.30 0.12 Piezoelectric constant g₃₃ × 10⁻³ V · m/N 2.7 2.8 1.3 1.50.6 Relative permittivity 23.1 22.4 22.0 22.3 22.8 Dielectric loss 0.0060.007 0.007 0.007 0.007

Production Example 1-1 <Production of Small-Particle Size Filler>

With the target composition of each element being set so that sodium was25.00 mol %, potassium was 25.00 mol %, niobium was 50.00 mol %, theratio ((Li+Na+K)/Nb) of alkali metals to niobium was 1.000, and theratio (K/(Na+K)) of potassium to the total amount of sodium andpotassium was 0.500, 4485 g of niobium pentoxide (Nb₂O₅, manufactured byJiujiang Tanbre Co., Ltd.), 893 g of sodium carbonate (Na₂CO₃,manufactured by Tokuyama Corporation), and 1160 g of potassium carbonate(fine powder for food additives K₂CO₃, manufactured by Nippon Soda Co.,Ltd.) were dry-mixed using a Henschel mixer (FM-20B, manufactured byNIPPON COKE & ENGINEERING CO., LTD.) under conditions of 2000 rpm and2.5 minutes, to obtain a first firing raw material.

The first firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.). After cooling to room temperature, it was groundusing a jet mill (STJ-200, manufactured by Seishin Enterprise Co., Ltd.)under conditions of a processing speed of 6 kg/h, an introductionpressure of 0.6 MPa, and a grinding pressure of 0.5 MPa, to obtain afirst ground product.

As a result of analyzing the composition of each element of the firstground product by fluorescent X-ray, sodium was 25.18 mol %, potassiumwas 24.57 mol %, niobium was 50.25 mol %, the ratio ((Na+K)/Nb) ofalkali metals to niobium was 0.990, and the ratio (K/(Na+K)) ofpotassium to the total alkali metals was 0.494.

In order to finely adjust the ratio ((Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to the totalalkali metals to 0.500, 27 g of potassium carbonate was added to 5500 gof the first ground product, followed by dry-mixing using a Henschelmixer under conditions of 2000 rpm and 3 minutes, to obtain a secondfiring raw material.

The second firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace. After cooling to roomtemperature, it was ground using a jet mill under conditions of aprocessing speed of 10 kg/h, an introduction pressure of 0.6 MPa, and agrinding pressure of 0.5 MPa, to obtain a second ground product.

As a result of analyzing the composition of the second ground product byfluorescent X-ray, sodium was 25.10%, potassium was 24.95 mol %, niobiumwas 49.96 mol %, the ratio ((Na+K)/Nb) of alkali metals to niobium was1.002, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.498.

In order to further enhance the crystallization, the second groundproduct was fired at 900° C. for 15 hours using an elevating electricfurnace. After cooling to room temperature, it was ground using a jetmill under conditions of a processing speed of 5 kg/h, an introductionpressure of 0.30 MPa, and a grinding pressure of 0.15 MPa, to obtainpotassium sodium niobate particles.

<Analysis>

As a result of analyzing the composition of the obtained potassiumsodium niobate (small-particle size) using ZSX100e, manufactured byRigaku Corporation, the ratio ((Na+K)/Nb) of alkali metals to niobiumwas 0.999, and the ratio (K/(Na+K)) of potassium to the total alkalimetals was 0.498.

Further, the obtained potassium sodium niobate (small-particle size) wassubjected to X-ray diffraction analysis (XRD) using UltimaIV,manufactured by Rigaku Corporation, and scanning electron microscopy(SEM) using S-4800, manufactured by Hitachi High-TechnologiesCorporation. The results are shown in FIG. 3 and FIG. 4.

From the XRD chart of FIG. 3, it was confirmed that the obtainedpotassium sodium niobate (small-particle size) was in a single phase.

Further, the D10, D50 (average particle size), and D90 of the obtainedpotassium sodium niobate (small-particle size) were measured usingMT-3300EXII, manufactured by MicrotracBEL Corp. As a result, the D10 was0.52 μm, the D50 was 0.67 μm, the D90 was 0.92 μm, and the SPAN((D90−D10)/D50) was 0.60. Further, the obtained particle sizedistribution curve is shown in FIG. 5.

Further, the BET specific surface area of the obtained potassium sodiumniobate (small-particle size) was measured using Macsorb HM model-1208,manufactured by Mountech Co., Ltd. As a result, the BET specific surfacearea was 4.65 m²/g.

Production Example 1-2 <Production of Small-Particle Size Filler>

The same procedure as in Production Example 1-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang TanbreCo., Ltd.), 937 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1108 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 26.25 mol %, potassium was 23.75 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.475, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 2.

Preparation Example 1-3 <Production of Small-Particle Size Filler>

The same procedure as in Preparation Example 1-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang TanbreCo., Ltd.), 981 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1050 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 27.50 mol %, potassium was 22.50 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.450, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 2.

Preparation Example 1-4 <Production of Small-Particle Size Filler>

The same procedure as in Preparation Example 1-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang TanbreCo., Ltd.), 1026 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 991 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 28.75 mol %, potassium was 21.25 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.425, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 2.

Production Example 1-5 <Production of Small-Particle Size Filler>

3512 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co.,Ltd.), 668 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 820 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were put into aHenschel mixer (FM-20B, manufactured by NIPPON COKE & ENGINEERING CO.,LTD). At this time, in the put raw materials, sodium was 24.88 mol %,potassium was 23.44 mol %, niobium was 51.68 mol %, the ratio((Li+Na+K)/Nb) of alkali metals to niobium was 0.935, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.485, in terms ofatoms. Subsequently, niobium pentoxide, sodium carbonate, and potassiumcarbonate put therein were dry-mixed using a Henschel mixer underconditions of 2000 rpm and 2.5 minutes, to obtain a first firing rawmaterial.

The first firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.) (first firing). After cooling to room temperature,it was ground using a jet mill (STJ-200, manufactured by SeishinEnterprise Co., Ltd.) under conditions of a processing speed of 6 kg/h,an introduction pressure of 0.6 MPa, and a grinding pressure of 0.5 MPa,to obtain a first ground product.

As a result of analyzing the composition of the first ground product byfluorescent X-ray, sodium was 24.90 mol %, potassium was 23.32 mol %,niobium was 51.78 mol %, the ratio ((Li+Na+K)/Nb) of alkali metalelements to niobium was 0.931, and the ratio (K/(Na+K)) of potassium tosodium and potassium was 0.484.

In order to finely adjust the ratio ((Li+Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to sodium andpotassium to 0.485, 54.7 g of lithium carbonate (Na₂CO₃, manufactured byGanfeng Lithium Co. Ltd.), 4.4 g of sodium carbonate, and 9.6 g ofpotassium carbonate were added to 4210 g of the first ground product,followed by dry-mixing using a Henschel mixer under conditions of 2000rpm and 3 minutes, to obtain a second firing raw material.

The second firing raw material thus obtained was fired at 550° C. for 7hours using an elevating electric furnace (second firing). After coolingto room temperature, it was ground using a jet mill under conditions ofa processing speed of 10 kg/h, an introduction pressure of 0.6 MPa, anda grinding pressure of 0.5 MPa, to obtain a second ground product.

As a result of analyzing sodium, potassium, and niobium in thecomposition of the second ground product by fluorescent X-ray, sodiumwas 24.92 mol %, potassium was 23.51 mol %, niobium was 51.57 mol %, themolar ratio ((Na+K)/Nb) of the total amount of sodium and potassium toniobium was 0.939, and the molar ratio (K/(Na+K)) of potassium to sodiumand potassium was 0.486. Further, the molar ratio of lithium to niobium,as determined by measuring the content of each of lithium and niobium byICP-AES analysis, was 0.06. From these results, the ratio ((Li+Na+K)/Nb)of alkali metals to niobium was calculated at 0.999, and the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the number of molesof the alkali metals was calculated at 0.060.

In order to further enhance the crystallinity, the second ground productwas fired at 900° C. for 10 hours using an elevating electric furnace(third firing). After cooling to room temperature, it was ground using ajet mill under conditions of a processing speed of 5 kg/h, anintroduction pressure of 0.30 MPa, and a grinding pressure of 0.15 MPa,to obtain lithium potassium sodium niobate particles.

<Analysis>

As a result of analyzing the components excluding lithium in thecomposition of the obtained lithium potassium sodium niobate byfluorescent X-ray using ZSX100e, manufactured by Rigaku Corporation,sodium was 24.92 mol %, potassium was 23.52 mol %, niobium was 51.56 mol%, the molar ratio ((Na+K)/Nb) of the total amount of sodium andpotassium to niobium was 0.939, and the molar ratio (K/(Na+K)) ofpotassium to sodium and potassium was 0.486. Further, the molar ratio oflithium to niobium, as determined by measuring the content of each oflithium and niobium by ICP-AES analysis using ICPS-8100CL, manufacturedby SHIMADZU CORPORATION, was 0.06. Therefore, the ratio ((Li+Na+K)/Nb)of alkali metals to niobium was calculated at 0.999, and the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the number of molesof the alkali metals was calculated at 0.060, finally, as a result ofwhich it was confirmed that the components reached the respective targetcompositions.

Further, the obtained lithium potassium sodium niobate was subjected toX-ray diffraction analysis (XRD) using UltimaIV, manufactured by RigakuCorporation, and scanning electron microscopy (SEM) using S-4800,manufactured by Hitachi High-Technologies Corporation. The results areshown in FIG. 10 and FIG. 11.

From the XRD chart of FIG. 10, it was confirmed that the obtainedlithium potassium sodium niobate was in a single phase.

Further, the D10, D50 (average particle size), and D90 of the obtainedlithium potassium sodium niobate were measured using MT-3300EXII,manufactured by MicrotracBEL Corp. As a result, the D10 was 0.57 μm, theD50 was 0.98 μm, the D90 was 1.59 μm, and the SPAN ((D90−D10)/D50) was1.05. Further, the obtained particle size distribution curve is shown inFIG. 12.

Further, the BET specific surface area of the obtained lithium potassiumsodium niobate was measured using Macsorb HM model-1208, manufactured byMountech Co., Ltd. As a result, the BET specific surface area was 2.67m²/g.

Production Example 2-1 <Production of Large-Particle Size Filler>

With the target composition of each element as an oxide being set sothat sodium was 25.00 mol %, potassium was 25.00 mol %, niobium was50.00 mol %, the ratio ((Na+K)/Nb) of alkali metals to niobium was1.000, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.500, 4800 g of niobium pentoxide (Nb₂O₅, manufactured by SANWAKAKO CO., LTD.), 960 g of sodium carbonate (Na₂CO₃, manufactured byTokuyama Corporation), and 1254 g of potassium carbonate (fine powderfor food additives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) weredry-mixed using a Henschel mixer (FM-20B, manufactured by NIPPON COKE &ENGINEERING CO., LTD.) under conditions of 2000 rpm and 2.5 minutes, toobtain a first firing raw material.

The first firing raw material thus obtained was fired at 700° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.). After cooling to room temperature, it was groundusing a jet mill (STJ-200, manufactured by Seishin Enterprise Co., Ltd.)under conditions of a processing speed of 10 kg/h, an introductionpressure of 0.3 MPa, and a grinding pressure of 0.15 MPa, to obtain afirst ground product.

As a result of analyzing the composition of each element of the firstground product as an oxide by fluorescent X-ray, sodium was 25.19 mol %,potassium was 24.75 mol %, niobium was 50.06 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 0.997, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.496.

In order to finely adjust the ratio ((Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to the totalalkali metals to 0.500, 6 g of potassium carbonate was added to 6000 gof the first ground product, followed by dry-mixing using a Henschelmixer under conditions of 2000 rpm and 3 minutes, to obtain a secondfiring raw material.

The second firing raw material thus obtained was fired at 700° C. for 7hours using an elevating electric furnace. After cooling to roomtemperature, it was ground using a jet mill under conditions of aprocessing speed of 10 kg/h, an introduction pressure of 0.3 MPa, and agrinding pressure of 0.15 MPa, to obtain a second ground product.

As a result of analyzing the composition of the second ground product byfluorescent X-ray, sodium was 25.11%, potassium was 24.86 mol %, niobiumwas 50.03 mol %, the ratio ((Na+K)/Nb) of alkali metals to niobium was0.999, and the ratio (K/(Na+K)) of potassium to the total alkali metalswas 0.497.

In order to further enhance the crystallization, the second groundproduct was fired at 900° C. for 15 hours using an elevating electricfurnace. After cooling to room temperature, it was ground using a jetmill under conditions of a processing speed of 10 kg/h, an introductionpressure of 0.30 MPa, and a grinding pressure of 0.15 MPa, to obtainpotassium sodium niobate particles.

<Analysis>

As a result of analyzing the composition of the obtained potassiumsodium niobate (large-particle size), the ratio ((Na+K)/Nb) of alkalimetals to niobium was 0.999, and the ratio (K/(Na+K)) of potassium tothe total alkali metals was 0.497.

Further, the obtained potassium sodium niobate (large-particle size) wassubjected to X-ray diffraction analysis (XRD) and scanning electronmicroscopy (SEM). The results are shown in FIG. 6 and FIG. 7.

From the XRD chart of FIG. 6, it was confirmed that the obtainedpotassium sodium niobate (large-particle size) was in a single phase.

Further, in the obtained potassium sodium niobate (large-particle size),the D10 was 4.97 μm, the D50 was 10.25 μm, the D90 was 16.49 μm, and theSPAN ((D90−D10)/D50) was 1.12. Further, the obtained particle sizedistribution curve is shown in FIG. 8.

Further, the BET specific surface area of the obtained potassium sodiumniobate (large-particle size) was 1.06 m²/g.

Production Example 2-2 <Production of Large-Particle Size Filler>

The same procedure as in Production Example 2-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by SANWA KAKO CO.,LTD.), 937 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1108 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 26.25 mol %, potassium was 23.75 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.475, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 3.

Preparation Example 2-3 <Production of Large-Particle Size Filler>

The same procedure as in Preparation Example 2-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by SANWA KAKO CO.,LTD.), 981 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1050 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 27.50 mol %, potassium was 22.50 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.450, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 3.

Preparation Example 2-4 <Production of Large-Particle Size Filler>

The same procedure as in Preparation Example 1-1 was performed exceptthat 4485 g of niobium pentoxide (Nb₂O₅, manufactured by SANWA KAKO CO.,LTD.), 1026 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 991 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials, in order to set the target composition of each element sothat sodium was 8.75 mol %, potassium was 21.25 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals was 0.425, instead ofsodium being 25.00 mol %, potassium being 25.00 mol %, and the ratio(K/(Na+K)) of potassium to the total alkali metals being 0.500.

Various properties of the obtained potassium sodium niobate are shown inTable 3.

Preparation Example 2-5 <Production of Large-Particle Size Filler>

3503 g of niobium pentoxide (Nb₂O₅, manufactured by SANWA KAKO CO.,LTD.), 672 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 825 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were put into aHenschel mixer (FM-20B, manufactured by NIPPON COKE & ENGINEERING CO.,LTD). At this time, in the put raw materials, sodium was 24.88 mol %,potassium was 23.44 mol %, niobium was 51.68 mol %, the ratio((Li+Na+K)/Nb) of alkali metals to niobium was 0.935, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.485, in terms ofatoms. Subsequently, niobium pentoxide, sodium carbonate, and potassiumcarbonate put therein were dry-mixed using a Henschel mixer underconditions of 2000 rpm and 2.5 minutes, to obtain a first firing rawmaterial.

The first firing raw material thus obtained was fired at 700° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.) (first firing). After cooling to room temperature,it was ground using a jet mill (STJ-200, manufactured by SeishinEnterprise Co., Ltd.) under conditions of a processing speed of 10 kg/h,an introduction pressure of 0.30 MPa, and a grinding pressure of 0.15MPa, to obtain a first ground product.

As a result of analyzing the composition of the first ground product byfluorescent X-ray, sodium was 25.21 mol %, potassium was 23.05 mol %,niobium was 51.74 mol %, the ratio ((Li+Na+K)/Nb) of alkali metalelements to niobium was 0.933, and the ratio (K/(Na+K)) of potassium tosodium and potassium was 0.478.

In order to finely adjust the ratio ((Li+Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to sodium andpotassium to 0.480, 52.6 g of lithium carbonate (Na₂CO₃, manufactured byGanfeng Lithium Co. Ltd.), 1.9 g of sodium carbonate, and 9.3 g ofpotassium carbonate were added to 4000 g of the first ground product,followed by dry-mixing using a Henschel mixer under conditions of 2000rpm and 3 minutes, to obtain a second firing raw material.

The second firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace. After cooling to roomtemperature, it was ground using a jet mill under conditions of aprocessing speed of 10 kg/h, an introduction pressure of 0.3 MPa, and agrinding pressure of 0.15 MPa, to obtain a second ground product.

As a result of analyzing sodium, potassium, and niobium in thecomposition of the second ground product by fluorescent X-ray, sodiumwas 25.22 mol %, potassium was 23.27 mol %, niobium was 51.51 mol %, andthe molar ratio (K/(Na+K)) of potassium to sodium and potassium was0.480. Further, the molar ratio of lithium to niobium, as determined bymeasuring the content of each of lithium and niobium by ICP-AESanalysis, was 0.06. From these results, the ratio ((Li+Na+K)/Nb) ofalkali metals to niobium was calculated at 1.001, and the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the number of molesof the alkali metals was calculated at 0.060.

In order to further enhance the crystallinity, the second ground productwas fired at 900° C. for 10 hours using an elevating electric furnace(third firing). After cooling to room temperature, it was ground using ajet mill under conditions of a processing speed of 10 kg/h, anintroduction pressure of 0.30 MPa, and a grinding pressure of 0.15 MPa,to obtain lithium potassium sodium niobate particles.

<Analysis>

As a result of analyzing the components excluding lithium in thecomposition of the obtained lithium potassium sodium niobate byfluorescent X-ray using ZSX100e, manufactured by Rigaku Corporation,sodium was 25.23 mol %, potassium was 23.25 mol %, niobium was 51.52 mol%, the molar ratio ((Na+K)/Nb) of the total amount of sodium andpotassium to niobium was 0.941, and the molar ratio (K/(Na+K)) ofpotassium to sodium and potassium was 0.480. Further, the molar ratio oflithium to niobium, as determined by measuring the content of each oflithium and niobium by ICP-AES analysis using ICPS-8100CL, manufacturedby SHIMADZU CORPORATION, was 0.06. Therefore, the ratio ((Li+Na+K)/Nb)of alkali metals to niobium was calculated at 0.999, and the ratio(Li/(Li+Na+K)) of the number of moles of lithium to the number of molesof the alkali metals was calculated at 0.060, finally, as a result ofwhich it was confirmed that the components reached the respective targetcompositions.

Further, the obtained lithium potassium sodium niobate was subjected toX-ray diffraction analysis (XRD) using UltimaIV, manufactured by RigakuCorporation, and scanning electron microscopy (SEM) using S-4800,manufactured by Hitachi High-Technologies Corporation. The results areshown in FIG. 13 and FIG. 14.

From the XRD chart of FIG. 13, it was confirmed that the obtainedlithium potassium sodium niobate was in a single phase.

Further, the D10, D50 (average particle size), and D90 of the obtainedlithium potassium sodium niobate were measured using MT-3300EXII,manufactured by MicrotracBEL Corp. As a result, the D10 was 5.37 μm, theD50 was 10.71 μm, the D90 was 17.07 μm, and the SPAN ((D90−D10)/D50) was1.09. Further, the obtained particle size distribution curve is shown inFIG. 15.

Further, the BET specific surface area of the obtained lithium potassiumsodium niobate was measured using Macsorb HM model-1208, manufactured byMountech Co., Ltd. As a result, the BET specific surface area was 0.66m²/g.

<Preparation of Mixed Composite Piezoelectric Material Filler>

The small-particle size potassium sodium niobate obtained in ProductionExample 1-1 and the large-particle size potassium sodium niobateobtained in Production Example 2-1 were mixed at a volume ratio of 40:60(large-particle size:small-particle size), to obtain a compositepiezoelectric material filler A.

Likewise, a mixed composite piezoelectric material filler B was obtainedby combining Production Example 1-2 and Production Example 2-2, a mixedcomposite piezoelectric material filler C was obtained by combiningProduction Example 1-3 and Production Example 2-3, a mixed compositepiezoelectric material filler D was obtained by combining ProductionExample 1-4 and Production Example 2-4, and mixed compositepiezoelectric material fillers E and F were obtained by combiningProduction Example 1-5 and Production Example 2-5.

Subsequently, the particle size distributions of the obtained mixedcomposite piezoelectric material fillers A to F were measured. Theparticle size distribution curve of the mixed composite piezoelectricmaterial filler A is shown in FIG. 9. The obtained particle sizedistribution curve showed a bimodal particle size distribution having afirst peak on the small-particle size side and a second peak on thelarge-particle size side, where the peak top of the first peak waslocated at 0.69 μm, and the peak top of the second peak was located at11.00 μm. Likewise, the particle size distribution curve of the mixedcomposite piezoelectric material filler E is shown in FIG. 16, and theparticle size distribution curve of the mixed composite piezoelectricmaterial filler is shown in FIG. 17. Each of them showed a bimodalparticle size distribution having a first peak on the small-particlesize side and a second peak on the large-particle size side. Variousproperties of them are shown in Table 4.

TABLE 2 Production Production Production Production ProductionSmall-particle size filler Example 1-1 Example 1-2 Example 1-3 Example1-4 Example 1-5 (Li + K + Na)/Nb Molar ratio 0.999 1.001 0.999 1.0010.999 K/(K + Na) Molar ratio 0.498 0.473 0.448 0.423 0.486 XRD Singlephase Single phase Single phase Single phase Single phase Averageparticle size (D50) μm 0.67 0.68 0.67 0.68 0.98 D10 0.52 0.52 0.52 0.510.57 D90 0.92 0.94 0.94 0.95 1.59 SPAN 0.60 0.62 0.62 0.64 1.05 BETspecific surface area m³/g 4.65 4.61 4.76 4.74 2.67

TABLE 3 Production Production Production Production ProductionLarge-particle size filler Example 2-1 Example 2-2 Example 2-3 Example2-4 Example 2-5 (Li + K + Na)/Nb Molar ratio 0.999 1.000 1.000 0.9991.001 K/(K + Na) Molar ratio 0.497 0.474 0.445 0.422 0.480 XRD Singlephase Single phase Single phase Single phase Single phase Averageparticle size (D50) μm 10.25 10.23 10.33 10.30 10.71 D10 4.97 5.05 5.215.09 5.37 D90 16.49 16.37 16.56 16.54 17.07 SPAN 1.12 1.11 1.10 1.111.09 BET specific surface area m³/g 1.06 1.02 1.06 1.02 0.66

TABLE 4 Composite piezoelectric material filler A B C D E FSmall-particle size filler Production Production Production ProductionProduction Production Example 1-1 Example 1-2 Example 1-3 Example 1-4Example 1-5 Example 1-5 Large-particle size filler Production ProductionProduction Production Production Production Example 2-1 Example 2-2Example 2-3 Example 2-4 Example 2-5 Example 2-5 Volume ratio(large-particle 40:60 40:60 40:60 40:60 40:60 60:40 size:small-particlesize) First peak top position (μm)  0.69  0.69  0.69  0.69  1.06  1.06Second peak top position (μm) 11.00 11.00 11.00 11.00 12.00 12.00 B/A* 0.39  0.39  0.39  0.39  0.35  0.94 *A: Frequency (%) of the particlesize at the first peak top, and B: Frequency (%) of the particle size atthe second peak top

Examples 11 to 20 <Fabrication of Composite Piezoelectric Material andComposite Piezoelectric Device>

A composite piezoelectric material filler was kneaded with an epoxyresin so that the volume fractions of the polymer matrix and thecomposite piezoelectric material filler were as shown in Table 5, toobtain an epoxy resin composition. The epoxy resin used herein wascomposed of 99 mass % of a thermosetting epoxy resin (product name: JER®828EL, manufactured by Mitsubishi Chemical Corporation, with a molecularweight of about 370, a specific gravity of 1.17, and a nominal viscosityat 25° C. of 120 to 150P), and 1 mass % of an imidazole curingaccelerator (product name: 2E4MZ, manufactured by SHIKOKU CHEMICALSCORPORATION). The obtained epoxy resin composition was cured at 140° C.for 5 hours to fabricate a plate composite piezoelectric material with athickness of 0.6 mm. Subsequently, 30-nm thick platinum films wereformed as electrodes on both surfaces of the obtained compositepiezoelectric material by vapor deposition, and thereafter −8.0 kV wasapplied thereto using a corona discharge system (ELC-01N, manufacturedby ELEMENT Co., Ltd.) for 30 minutes, to obtain a compositepiezoelectric device polarized in the thickness direction.

The piezoelectric constant (d₃₃), the relative permittivity, and thedielectric loss of the obtained composite piezoelectric device weremeasured by the following measurement methods. Further, thepiezoelectric constant (g₃₃) was determined by calculation using thepiezoelectric constant (d₃₃) and the relative permittivity obtained. Theresults are shown in Table 5.

(Measurement Method)

<Piezoelectric Constant (d₃₃)>

The composite piezoelectric device was set in the force head of apiezometer system (PM200, manufactured by Piezo Test Ltd.) in thethickness direction, and the static force was adjusted to 5 N. The d₃₃was measured with a vibration frequency of 110 Hz and a force of 0.25 N.

<Relative Permittivity and Dielectric Loss>

Using an impedance analyzer (1255B, manufactured by SolartronAnalytical) and an interface (1296, manufactured by SolartronAnalytical), the relative permittivity and the dielectric loss at afrequency of 100 Hz and an applied voltage of 1 V were measured.

TABLE 5 Example Example Example Example Example Example Example ExampleExample Example 11 12 13 14 15 16 17 18 19 20 Composite piezoelectricmaterial Composite piezoelectric A B C D A B C D E F material fillerFiller content (vol %) 40   40   40   40   50   50   50   50   50   50  Matrix (vol %) 60   60   60   60   50   50   50   50   50   50  Composite piezoelectric device Piezoelectric constant d₃₃  2.92  3.45 1.59  0.85  6.72  7.31  3.51  1.21  3.30  5.48 pC/N Piezoelectricconstant g₃₃ × 11.6  13.9  6.3 3.5 17.3  19.9  9.4 3.7 9.1 12.4  10⁻³V ·m/N Relative permittivity 28.4  28.0  28.7  27.1  43.8  41.5  42.2 37.2  41.1  49.9  Dielectric loss   0.007   0.007   0.008   0.007  0.010   0.009   0.009   0.007   0.009   0.012

Examples 21 to 26 <Fabrication of Composite Piezoelectric Material andComposite Piezoelectric Device>

The small-particle size filler and the large-particle size fillerobtained in each of Production Examples were kneaded with a polymermatrix, so that the volume fractions of the small-particle size fillerand the large-particle size filler were as shown in Table 6, by firstkneading the small-particle size filler with an epoxy resin and thenkneading the large-particle size filler, to obtain an epoxy resincomposition. The epoxy resin used herein was composed of 99 mass % of athermosetting epoxy resin (product name: JER® 828EL, manufactured byMitsubishi Chemical Corporation, with a molecular weight of about 370, aspecific gravity of 1.17, and a nominal viscosity at 25° C. of 120 to150P), and 1 mass % of an imidazole curing accelerator (product name:2E4MZ, manufactured by SHIKOKU CHEMICALS CORPORATION). The obtainedepoxy resin composition was cured at 140° C. for 5 hours to fabricate aplate composite piezoelectric material with a thickness of 0.6 mm.Subsequently, 30-nm thick platinum films were formed as electrodes onboth surfaces of the obtained composite piezoelectric material by vapordeposition, and thereafter −8.0 kV was applied thereto using a coronadischarge system (ELC-01N, manufactured by ELEMENT Co., Ltd.) for 30minutes, to obtain a composite piezoelectric device polarized in thethickness direction.

The piezoelectric constant (d₃₃), the relative permittivity, and thedielectric loss of the obtained composite piezoelectric device weremeasured by the following measurement methods. Further, thepiezoelectric constant (g₃₃) was determined by calculation using thepiezoelectric constant (d₃₃) and the relative permittivity obtained. Theresults are shown in Table 6.

TABLE 6 Example 21 Example 22 Example 23 Example 24 Example 25 Example26 Composite piezoelectric material Small-particle size fillerProduction Production Production Production Production ProductionExample Example Example Example Example Example 1-1 1-2 1-3 1-4 1-5 1-5Large-particle size filler Production Production Production ProductionProduction Production Example Example Example Example Example Example2-1 2-2 2-3 2-4 2-5 2-5 Volume ratio (large-particle 40:60 40:60 40:6040:60 40:60 60:40 size:small-particle size) Filler content (vol %) 40  40   40   40   50   50   Matrix (vol %) 60   60   60   60   50   50  Composite piezoelectric device Piezoelectric constant d₃₃ pC/N  3.00 3.50  1.79  0.81  3.45  5.75 Piezoelectric constant g₃₃ × 11.8  14.1 7.0 3.4 9.4 12.8  10⁻³V · m/N Relative permittivity 28.6  28.1  28.9 26.8  41.6  50.6  Dielectric loss   0.007   0.008   0.007   0.007  0.009   0.013

Comparative Examples 11 to 18 <Fabrication of Composite PiezoelectricMaterial and Composite Piezoelectric Device>

The small-particle size filler or the large-particle size fillerobtained in each of Production Examples was kneaded with an epoxy resinso that the volume fractions of the small-particle size filler or thelarge-particle size filler and the polymer matrix were as shown in Table7, to obtain an epoxy resin composition. The epoxy resin used herein wascomposed of 99 mass % of a thermosetting epoxy resin (product name: JER®828EL, manufactured by Mitsubishi Chemical Corporation, with a molecularweight of about 370, a specific gravity of 1.17, and a nominal viscosityat 25° C. of 120 to 150P), and 1 mass % of an imidazole curingaccelerator (product name: 2E4MZ, manufactured by SHIKOKU CHEMICALSCORPORATION). The obtained epoxy resin composition was cured at 140° C.for 5 hours to fabricate a plate composite piezoelectric material with athickness of 0.6 mm. Subsequently, 30-nm thick platinum films wereformed as electrodes on both surfaces of the obtained compositepiezoelectric material by vapor deposition, and thereafter −8.0 kV wasapplied thereto using a corona discharge system (ELC-01N, manufacturedby ELEMENT Co., Ltd.) for 30 minutes, to obtain a compositepiezoelectric device polarized in the thickness direction.

The piezoelectric constant (d₃₃), the relative permittivity, and thedielectric loss of the obtained composite piezoelectric device weremeasured by the following measurement methods. Further, thepiezoelectric constant (g₃₃) was determined by calculation using thepiezoelectric constant (d₃₃) and the relative permittivity obtained. Theresults are shown in Table 7.

TABLE 7 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Comparative Example 11 Example12 Example 13Example 14 Example 15 Example 16 Example 17 Example 18 Compositepiezoelectric material Filler used Production Production ProductionProduction Production Production Production Production Example 1-1Example 1-2 Example 1-3 Example 1-4 Example 2-1 Example 2-2 Example 2-3Example 2-4 Filler content 40   40   40   40   25   25   25   25   (vol%) Matrix (vol %) 60   60   60   60   75   75   75   75   CompositeDevice × Device × Device × Device × piezoelectric device Piezoelectric 0.26  0.55  0.30  0.12 constant d₃₃ pC/N Piezoelectric 1.3 2.7 1.5 0.6constant g₃₃ × 10⁻³V · m/N Relative 22.0  23.1  22.3  22.8  permittivityDielectric loss   0.007   0.006   0.007   0.007 *) In the table, ″Device×″ indicates that kneading of the epoxy resin and the filler wasdifficult, making it impossible to fabricate any device. *) In thetable, ″Device ×″ indicates that kneading of the epoxy resin and thefiller was difficult, making it impossible to fabricate any device.

Example 31 <Production of Potassium Sodium Niobate>

4485 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co.,Ltd.), 893 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1160 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were put into aHenschel mixer (FM-20B, manufactured by NIPPON COKE & ENGINEERING CO.,LTD). At this time, in the put raw materials, sodium was 25.00 mol %,potassium was 25.00 mol %, niobium was 50.00 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 1.000, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.500, in terms ofatoms. Subsequently, niobium pentoxide, sodium carbonate, and potassiumcarbonate put therein were dry-mixed using a Henschel mixer underconditions of 2000 rpm and 2.5 minutes, to obtain a first firing rawmaterial.

The first firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.) (first firing). After cooling to room temperature,it was ground using a jet mill (STJ-200, q Seishin Enterprise Co., Ltd.)under conditions of a processing speed of 6 kg/h, an introductionpressure of 0.6 MPa, and a grinding pressure of 0.5 MPa, to obtain afirst ground product.

As a result of analyzing the composition of the first ground product byfluorescent X-ray, sodium was 25.18 mol %, potassium was 24.57 mol %,niobium was 50.25 mol %, the ratio ((Na+K)/Nb) of alkali metals toniobium was 0.990, and the ratio (K/(Na+K)) of potassium to sodium andpotassium was 0.494.

In order to finely adjust the ratio ((Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to sodium andpotassium to 0.500, 27 g of potassium carbonate was added to 5500 g ofthe first ground product, followed by dry-mixing using a Henschel mixerunder conditions of 2000 rpm and 3 minutes, to obtain a second firingraw material.

The second firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (second firing). After coolingto room temperature, it was ground using a jet mill under conditions ofa processing speed of 10 kg/h, an introduction pressure of 0.6 MPa, anda grinding pressure of 0.5 MPa, to obtain a second ground product.

As a result of analyzing the composition of the second ground product byfluorescent X-ray, sodium was 25.10%, potassium was 24.95 mol %, niobiumwas 49.96 mol %, the ratio ((Na+K)/Nb) of alkali metals to niobium was1.002, and the ratio (K/(Na+K)) of potassium to sodium and potassium was0.498.

In order to further enhance the crystallinity, the second ground productwas fired at 900° C. for 15 hours using an elevating electric furnace(third firing). After cooling to room temperature, it was ground using ajet mill under conditions of a processing speed of 5 kg/h, anintroduction pressure of 0.30 MPa, and a grinding pressure of 0.15 MPa,to obtain potassium sodium niobate particles.

<Analysis>

As a result of analyzing the composition of the obtained potassiumsodium niobate by fluorescent X-ray using ZSX100e, manufactured byRigaku Corporation, the ratio ((Na+K)/Nb) of alkali metals to niobiumwas 0.999, and the ratio (K/(Na+K)) of potassium to the total alkalimetals was 0.498. From the aforementioned results, the difference from0.500 that was the ratio (K/(Na+K)) of potassium to sodium and potassiumin the first firing raw material was 0.002.

Further, the obtained potassium sodium niobate was subjected to X-raydiffraction analysis (XRD) using UltimaIV, manufactured by RigakuCorporation, and scanning electron microscopy (SEM) using S-4800,manufactured by Hitachi High-Technologies Corporation. The results areshown in FIG. 18 and FIG. 19.

From the XRD chart of FIG. 18, it was confirmed that the obtainedpotassium sodium niobate was in a single phase.

Further, the particle size distribution of the obtained potassium sodiumniobate was measured using MT-3300EXII, manufactured by MicrotracBELCorp. As a result, the average particle size D50 was 0.67 μm.

Further, the BET specific surface area of the obtained potassium sodiumniobate was measured using Macsorb HM model-1208, manufactured byMountech Co., Ltd. As a result, the BET specific surface area was 4.65m²/g.

Example 32

The same procedure as in Example 31 was performed except that 4485 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.),937 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1108 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials. At this time, in the put raw materials, sodium was 26.25 mol%, potassium was 23.75 mol %, niobium was 50.00 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 1.000, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.475, in terms ofatoms.

In the obtained potassium sodium niobate, the ratio ((Na+K)/Nb) ofalkali metals to niobium was 1.001, and the ratio (K/(Na+K)) ofpotassium to the total alkali metals was 0.473. From the aforementionedresults, the difference from 0.475 that was the ratio (K/(Na+K)) ofpotassium to sodium and potassium in the first firing raw material was0.002. Further, from the X-ray diffraction analysis, it was in a singlephase, the average particle size (D50) was 0.68 μm, and the BET specificsurface area was 4.61 m²/g.

Example 33

The same procedure as in Example 31 was performed except that 4485 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.),981 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 1050 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials. At this time, in the put raw materials, sodium was 27.50 mol%, potassium was 22.50 mol %, niobium was 50.00 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 1.000, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.450, in terms ofatoms.

In the obtained potassium sodium niobate, the ratio ((Na+K)/Nb) ofalkali metals to niobium was 0.999, and the ratio (K/(Na+K)) ofpotassium to the total alkali metals was 0.448. From the aforementionedresults, the difference from 0.450 that was the ratio (K/(Na+K)) ofpotassium to sodium and potassium in the first firing raw material was0.002. Further, from the X-ray diffraction analysis, it was in a singlephase, the average particle size (D50) was 0.67 μm, and the BET specificsurface area was 4.76 m²/g.

Example 34

The same procedure as in Example 31 was performed except that 4485 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.),1026 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 991 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were used as rawmaterials. At this time, in the put raw materials, sodium was 28.75 mol%, potassium was 21.25 mol %, niobium was 50.00 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 1.000, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.425, in terms ofatoms.

In the obtained potassium sodium niobate, the ratio ((Na+K)/Nb) ofalkali metals to niobium was 1.001, and the ratio (K/(Na+K)) ofpotassium to the total alkali metals was 0.424. From the aforementionedresults, the difference from 0.425 that was the ratio (K/(Na+K)) ofpotassium to sodium and potassium in the first firing raw material was0.001. Further, from the X-ray diffraction analysis, it was in a singlephase, the average particle size (D50) was 0.68 μm, and the BET specificsurface area was 4.74 m²/g.

Comparative Example 31

A firing raw material that was the same as the first firing raw materialof Example 31 was obtained.

The obtained firing raw material was fired at 900° C. for 15 hours usingan elevating electric furnace (SLV-6060L-SP, manufactured by MotoyamaCo., Ltd.). After cooling to room temperature, it was ground using a jetmill (STJ-200, manufactured by Seishin Enterprise Co., Ltd.) underconditions of a processing speed of 5 kg/h, an introduction pressure of0.30 MPa, and a grinding pressure of 0.15 MPa, to obtain potassiumsodium niobate particles.

In the obtained potassium sodium niobate, the ratio ((Na+K)/Nb) ofalkali metals to niobium was 0.987, and the ratio (K/(Na+K)) ofpotassium to sodium and potassium was 0.493, thus failing to achieve thetarget compositions. From the X-ray diffraction analysis, it wasconfirmed that the potassium sodium niobate was in a single phase, theaverage particle size (D50) was 0.96 μm, and the BET specific surfacearea was 2.93 m²/g.

Example 35

The same procedure as in Example 31 was performed except that 4983 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.) and1991 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation) were used as raw materials, the firing temperature in thefirst firing and the second firing was set to 570° C., and the firingtemperature in the third firing was set to 590° C. At this time, in thefirst firing raw material, sodium was 50.00 mol %, niobium was 50.00 mol%, the ratio (Na/Nb) of alkali metals to niobium was 1.000, and theratio (K/(Na+K)) of potassium to sodium and potassium was 0, in terms ofatoms.

In the obtained sodium niobate, the ratio (Na/Nb) of alkali metals toniobium was 1.001, and the ratio (K/(Na+K)) of potassium to sodium andpotassium was 0. Further, from the X-ray diffraction analysis, it was ina single phase, the average particle size (D50) was 0.61 μm, and the BETspecific surface area was 5.31 m²/g.

Example 36

The same procedure as in Example 31 was performed except that 2647 g ofniobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co., Ltd.) and1377 g of potassium carbonate (fine powder for food additives K₂CO₃,manufactured by Nippon Soda Co., Ltd.) were used as raw materials, thefiring conditions in the second firing were changed to 800° C. and 15 h,and the procedure up to the second grinding was performed. At this time,in the first firing raw material, potassium was 50.00 mol %, niobium was50.00 mol %, the ratio (K/Nb) of alkali metals to niobium was 1.000, andthe ratio (K/(Na+K)) of potassium to sodium and potassium was 1, interms of atoms.

In the obtained potassium niobate, the ratio (K/Nb) of alkali metals toniobium was 1.002, and the ratio (K/(Na+K)) of potassium to sodium andpotassium was 1.000. Further, from the X-ray diffraction analysis, itwas in a single phase, the average particle size (D50) was 0.64 μm, andthe BET specific surface area was 4.33 m²/g.

Example 37 <Production of Lithium Sodium Lithium Niobate>

3508 g of niobium pentoxide (Nb₂O₅, manufactured by Jiujiang Tanbre Co.,Ltd.), 670 g of sodium carbonate (Na₂CO₃, manufactured by TokuyamaCorporation), and 822 g of potassium carbonate (fine powder for foodadditives K₂CO₃, manufactured by Nippon Soda Co., Ltd.) were put into aHenschel mixer (FM-20B, manufactured by NIPPON COKE & ENGINEERING CO.,LTD). At this time, in the put raw materials, sodium was 24.44 mol %,potassium was 22.56 mol %, niobium was 50.00 mol %, the ratio((Na+K)/Nb) of alkali metals to niobium was 0.940, and the ratio(K/(Na+K)) of potassium to sodium and potassium was 0.480, in terms ofatoms. Subsequently, niobium pentoxide, sodium carbonate, and potassiumcarbonate put therein were dry-mixed using a Henschel mixer underconditions of 2000 rpm and 2.5 minutes, to obtain a first firing rawmaterial.

The first firing raw material thus obtained was fired at 650° C. for 7hours using an elevating electric furnace (SLV-6060L-SP, manufactured byMotoyama Co., Ltd.) (first firing). After cooling to room temperature,it was ground using a jet mill (STJ-200, manufactured by SeishinEnterprise Co., Ltd.) under conditions of a processing speed of 6 kg/h,an introduction pressure of 0.6 MPa, and a grinding pressure of 0.5 MPa,to obtain a first ground product.

As a result of analyzing the composition of the first ground product byfluorescent X-ray, sodium was 25.06 mol %, potassium was 23.28 mol %,niobium was 51.66 mol %, the ratio ((Li+Na+K)/Nb) of alkali metal toniobium was 0.936, and the ratio (K/(Na+K)) of potassium to sodium andpotassium was 0.482.

In order to finely adjust the ratio ((Li+Na+K)/Nb) of alkali metals toniobium to 1.000 and the ratio (K/(Na+K)) of potassium to sodium andpotassium to 0.480, 54.7 g of lithium carbonate (Li₂CO₃, manufactured byGanfeng Lithium Co. Ltd.), 5.0 g of sodium carbonate, and 0.9 g ofpotassium carbonate were added to 4217 g of the first ground product,followed by dry-mixing using a Henschel mixer under conditions of 2000rpm and 3 minutes, to obtain a second firing raw material.

The second firing raw material thus obtained was fired at 550° C. for 7hours using an elevating electric furnace (second firing). After coolingto room temperature, it was ground using a jet mill under conditions ofa processing speed of 10 kg/h, an introduction pressure of 0.6 MPa, anda grinding pressure of 0.5 MPa, to obtain a second ground product.

As a result of analyzing sodium, potassium, and niobium in thecomposition of the second ground product by fluorescent X-ray, sodiumwas 25.18 mol %, potassium was 23.25 mol %, niobium was 51.58 mol %, themolar ratio ((Na+K)/Nb) of the total amount of sodium and potassium toniobium was 0.939, the number of moles of potassium to the number ofmoles of sodium and potassium (K/(Na+K)) was 0.480. Further, the molarratio of lithium to niobium, as determined by measuring the content ofeach of lithium and niobium by ICP-AES analysis, was 0.06. From theseresults, the ratio ((Li+Na+K)/Nb) of alkali metals to niobium wascalculated at 0.999, and the ratio (Li/(Li+Na+K)) of the number of molesof lithium to the number of moles of the alkali metals was calculated at0.060.

In order to further enhance the crystallinity, the second ground productwas fired at 900° C. for 15 hours using an elevating electric furnace(third firing). After cooling to room temperature, it was ground using ajet mill under conditions of a processing speed of 5 kg/h, anintroduction pressure of 0.30 MPa, and a grinding pressure of 0.15 MPa,to obtain lithium potassium sodium niobate particles.

<Analysis>

As a result of analyzing the components excluding lithium in thecomposition of the obtained lithium potassium sodium niobate byfluorescent X-ray using ZSX100e, manufactured by Rigaku Corporation,sodium was 25.18%, potassium was 23.25 mol %, niobium was 51.58 mol %,the molar ratio ((Na+K)/Nb) of the total amount of sodium and potassiumto niobium was 0.939, and the number of moles of potassium to the numberof moles of sodium and potassium (K/(Na+K)) was 0.480. Further, themolar ratio of lithium to niobium, as determined by measuring thecontent of each of lithium and niobium by ICP-AES analysis usingICPS-8100CL, manufactured by SHIMADZU CORPORATION, was 0.06. Therefore,the ratio ((Li+Na+K)/Nb) of alkali metals to niobium was calculated at0.999, and the ratio (Li/(Li+Na+K)) of the number of moles of lithium tothe number of moles of the alkali metals was calculated at 0.060,finally, as a result of which it was confirmed that the componentsreached the respective target compositions.

Further, the obtained lithium potassium sodium niobate was subjected toX-ray diffraction analysis (XRD) using UltimaIV, manufactured by RigakuCorporation, and scanning electron microscopy (SEM) using S-4800,manufactured by Hitachi High-Technologies Corporation. The results areshown in FIG. 20 and FIG. 21.

From the XRD chart of FIG. 20, it was confirmed that the obtainedlithium potassium sodium niobate was in a single phase.

Further, the particle size distribution of the obtained lithiumpotassium sodium niobate was measured using MT-3300EXII, manufactured byMicrotracBEL Corp. As a result, the average particle size D50 was 1.01μm.

Further, the BET specific surface area of the obtained lithium potassiumsodium niobate was measured using Macsorb HM model-1208, manufactured byMountech Co., Ltd. As a result, the BET specific surface area was 2.63m²/g.

1. A composite piezoelectric material comprising: a polymer matrix; anda composite piezoelectric material filler dispersed in the polymermatrix, wherein the composite piezoelectric material filler comprises: asmall-particle size filler comprising an alkali niobate compound havinga ratio (K/(Na+K)) of the number of moles of potassium to the totalnumber of moles of sodium and potassium of 0.40 to 0.60 in terms ofatoms and a ratio ((Li+Na+K)/Nb) of the total number of moles of alkalimetal elements to the number of moles of niobium of 0.995 to 1.005 interms of atoms; and a large-particle size filler comprising an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium of 0.40to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total numberof moles of alkali metal elements to the number of moles of niobium of0.995 to 1.005 in terms of atoms, a total content of the small-particlesize filler and the large-particle size filler is 20 to 80 vol % basedon the entire composite piezoelectric material, the small-particle sizefiller has an average particle size (D50) of 0.1 to 1.2 μm, thelarge-particle size filler has an average particle size (D50) of 1 to 15μm, and a content ratio of the large-particle size filler to thesmall-particle size filler (large-particle size filler:small-particlesize filler) is 10:90 to 90:10 by volume.
 2. The composite piezoelectricmaterial according to claim 1, wherein the small-particle size fillerhas a BET specific surface area of 2 to 15 m²/g, and the large-particlesize filler has a BET specific surface area of 0.1 to 3 m²/g.
 3. Thecomposite piezoelectric material according to claim 1, wherein a ratio(large-particle size filler/small-particle size filler) of the averageparticle size (D50) of the large-particle size filler to the averageparticle size (D50) of the small-particle size filler is 2 to
 150. 4.The composite piezoelectric material according to claim 1, wherein aratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the small-particle sizefiller is 0 or more and less than 0.10 in terms of atoms, and a ratio(Li/(Li+Na+K)) of the number of moles of lithium to the total number ofmoles of alkali metal elements in the large-particle size filler is 0 ormore and less than 0.10 in terms of atoms.
 5. A composite piezoelectricdevice comprising: the composite piezoelectric material according toclaim 1 which has been polarized.
 6. A composite piezoelectric materialcomprising: a polymer matrix; and a composite piezoelectric materialfiller dispersed in the polymer matrix, wherein the compositepiezoelectric material filler comprises an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.40 to 0.60 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, a content of the alkali niobate compound is 20to 80 vol % based on the entire composite piezoelectric material, andthe alkali niobate compound exhibits a bimodal particle sizedistribution including a first peak having a peak top in a particle sizerange of 0.1 to 1.2 μm and a second peak having a peak top in a particlesize range of 1 to 15 μm in a particle size distribution measurement,wherein a ratio (B/A) of a value (B) of a frequency (%) of a particlesize at the peak top of the second peak to a value (A) of a frequency(%) of a particle size at the peak top of the first peak is 0.1 to 20.7. The composite piezoelectric material according to claim 6, wherein aratio (the particle size at the peak top of the second peak/the particlesize at the peak top of the first peak) of the particle size at the peaktop of the second peak to the particle size at the peak top of the firstpeak is 2 to
 150. 8. The composite piezoelectric material according toclaim 6, wherein a ratio (Li/(Li+Na+K)) of the number of moles oflithium to the total number of moles of alkali metal elements in thealkali niobate compound is 0 or more and less than 0.10 in terms ofatoms.
 9. A composite piezoelectric device comprising: the compositepiezoelectric material according to claim 6 which has been polarized.10. A composite piezoelectric material filler comprising a mixture of: asmall-particle size filler comprising an alkali niobate compound havinga ratio (K/(Na+K)) of the number of moles of potassium to the totalnumber of moles of sodium and potassium of 0.40 to 0.60 in terms ofatoms and a ratio ((Li+Na+K)/Nb) of the total number of moles of alkalimetal elements to the number of moles of niobium of 0.995 to 1.005 interms of atoms; and a large-particle size filler comprising an alkaliniobate compound having a ratio (K/(Na+K)) of the number of moles ofpotassium to the total number of moles of sodium and potassium of 0.40to 0.60 in terms of atoms and a ratio ((Li+Na+K)/Nb) of the total numberof moles of alkali metal elements to the number of moles of niobium of0.995 to 1.005 in terms of atoms, wherein the small-particle size fillerhas an average particle size (D50) of 0.1 to 1.2 μm, the large-particlesize filler has an average particle size (D50) of 1 to 15 μm, and amixing ratio (large-particle size filler:small-particle size filler) ofthe large-particle size filler to the small-particle size filler is10:90 to 90:10 by volume.
 11. The composite piezoelectric materialfiller according to claim 10, wherein the small-particle size filler hasa BET specific surface area of 2 to 15 m²/g, and the large-particle sizefiller has a BET specific surface area of 0.1 to 3 m²/g.
 12. Thecomposite piezoelectric material filler according to claim 10, wherein aratio (large-particle size filler/small-particle size filler) of theaverage particle size (D50) of the large-particle size filler to theaverage particle size (D50) of the small-particle size filler is 2 to150.
 13. The composite piezoelectric material filler according to claim10, wherein a ratio (Li/(Li+Na+K)) of the number of moles of lithium tothe total number of moles of alkali metal elements in the small-particlesize filler is 0 or more and less than 0.10 in terms of atoms, and aratio (Li/(Li+Na+K)) of the number of moles of lithium to the totalnumber of moles of alkali metal elements in the large-particle sizefiller is 0 or more and less than 0.10 in terms of atoms.
 14. Acomposite piezoelectric material comprising: the composite piezoelectricmaterial filler according to claim 10; and a polymer matrix.
 15. Acomposite piezoelectric device comprising: the composite piezoelectricmaterial according to claim 14 which has been polarized.
 16. A compositepiezoelectric material filler comprising: an alkali niobate compoundhaving a ratio (K/(Na+K)) of the number of moles of potassium to thetotal number of moles of sodium and potassium of 0.40 to 0.60 in termsof atoms and a ratio ((Li+Na+K)/Nb) of the total number of moles ofalkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, the composite piezoelectric material fillerexhibiting a bimodal particle size distribution including a first peakhaving a peak top in a particle size range of 0.1 to 1.2 μm and a secondpeak having a peak top in a particle size range of 1 to 15 μm in aparticle size distribution measurement, wherein a ratio (B/A) of a value(B) of a frequency (%) of a particle size at the peak top of the secondpeak to a value (A) of a frequency (%) of a particle size at the peaktop of the first peak is 0.1 to
 20. 17. The composite piezoelectricmaterial filler according to claim 16, wherein a ratio (Li/(Li+Na+K)) ofthe number of moles of lithium to the total number of moles of alkalimetal elements in the alkali niobate compound is 0 or more and less than0.10 in terms of atoms.
 18. The composite piezoelectric material filleraccording to claim 16, wherein a ratio (the particle size at the peaktop of the second peak/the particle size at the peak top of the firstpeak) of the particle size at the peak top of the second peak to theparticle size at the peak top of the first peak is 2 to
 150. 19. Acomposite piezoelectric material comprising: the composite piezoelectricmaterial filler according to claim 16; and a polymer matrix.
 20. Acomposite piezoelectric device comprising: the composite piezoelectricmaterial according to claim 19 which has been polarized.
 21. A compositepiezoelectric material filler used for the composite piezoelectricmaterial according to claim 1, the composite piezoelectric materialfiller comprising an alkali niobate compound having a ratio (K/(Na+K))of the number of moles of potassium to the total number of moles ofsodium and potassium of 0.40 to 0.60 in terms of atoms and a ratio((Li+Na+K)/Nb) of the total number of moles of alkali metal elements tothe number of moles of niobium of 0.995 to 1.005 in terms of atoms, andthe composite piezoelectric material filler having an average particlesize (D50) of 0.1 to 1.2 μm.
 22. The composite piezoelectric materialfiller according to claim 21, wherein a ratio (Li/(Li+Na+K)) of thenumber of moles of lithium to the total number of moles of alkali metalelements in the alkali niobate compound is 0 or more and less than 0.10in terms of atoms.
 23. A composite piezoelectric material filler usedfor the composite piezoelectric material according to claim 1, thecomposite piezoelectric material filler comprising an alkali niobatecompound having a ratio (K/(Na+K)) of the number of moles of potassiumto the total number of moles of sodium and potassium of 0.40 to 0.60 interms of atoms and a ratio ((Li+Na+K)/Nb) of the total number of molesof alkali metal elements to the number of moles of niobium of 0.995 to1.005 in terms of atoms, and the composite piezoelectric material fillerhaving an average particle size (D50) of 1 to 15 μm.
 24. The compositepiezoelectric material filler according to claim 23, wherein a ratio(Li/(Li+Na+K)) of the number of moles of lithium to the total number ofmoles of alkali metal elements in the alkali niobate compound is 0 ormore and less than 0.10 in terms of atoms.